U.S. patent application number 16/469984 was filed with the patent office on 2020-03-19 for multi-layered film , method for the production and use thereof.
The applicant listed for this patent is BASF SE. Invention is credited to Juergen Detering, Yannick Fuchs, Alejandra Garcia Marcos, Markus Meise, Benjamin Schmidt-Hansberg, Helmut Witteler.
Application Number | 20200086616 16/469984 |
Document ID | / |
Family ID | 60937713 |
Filed Date | 2020-03-19 |
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United States Patent
Application |
20200086616 |
Kind Code |
A1 |
Meise; Markus ; et
al. |
March 19, 2020 |
MULTI-LAYERED FILM , METHOD FOR THE PRODUCTION AND USE THEREOF
Abstract
Described herein is a multilayer film including at least one
layer including a polymer composition obtainable by free-radical
polymerization of a monomer composition including at least one
monomer A) selected from .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids, salts of .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids, anhydrides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids and mixtures thereof, where the free-radical polymerization
is effected in the presence of at least one polyether component.
Also described herein is a process for producing the multilayer
film, methods of using the multilayer film and a sheath or coating
for a washing composition, cleaning composition or dishwashing
composition portion including the multilayer film, and to washing
compositions, cleaning compositions or dishwashing compositions
including the multilayer film.
Inventors: |
Meise; Markus;
(Ludwigshafen, DE) ; Fuchs; Yannick;
(Ludwigshafen, DE) ; Witteler; Helmut;
(Ludwigshafen, DE) ; Garcia Marcos; Alejandra;
(Ludwigshafen, DE) ; Detering; Juergen;
(Ludwigshafen, DE) ; Schmidt-Hansberg; Benjamin;
(Ludwigshafen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
|
DE |
|
|
Family ID: |
60937713 |
Appl. No.: |
16/469984 |
Filed: |
December 15, 2017 |
PCT Filed: |
December 15, 2017 |
PCT NO: |
PCT/EP2017/083127 |
371 Date: |
June 14, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 2307/4023 20130101;
B32B 2439/40 20130101; B32B 2307/748 20130101; B32B 27/30 20130101;
C08J 7/0427 20200101; C11D 1/72 20130101; B32B 27/08 20130101; B32B
27/34 20130101; B32B 23/20 20130101; B32B 27/32 20130101; B32B 7/02
20130101; C08F 2/30 20130101; C11D 17/042 20130101; C08F 120/06
20130101; B32B 2439/00 20130101; B32B 27/308 20130101; C08F 20/06
20130101; B32B 2307/54 20130101; C11D 3/3707 20130101; B32B 27/28
20130101; B32B 27/285 20130101; C11D 3/3757 20130101; B32B 2307/412
20130101; B32B 2307/732 20130101; B32B 2553/00 20130101; B32B
27/306 20130101; B32B 23/08 20130101; B32B 2270/00 20130101; B32B
7/12 20130101; B32B 2250/24 20130101; B32B 23/22 20130101; B32B
27/302 20130101; B32B 2307/718 20130101 |
International
Class: |
B32B 27/30 20060101
B32B027/30; B32B 23/20 20060101 B32B023/20; B32B 23/22 20060101
B32B023/22; B32B 27/28 20060101 B32B027/28 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 16, 2016 |
EP |
16204778.1 |
Sep 6, 2017 |
EP |
17189675.6 |
Claims
1. A multilayer film comprising at least one layer comprising a
polymer composition P1) obtainable by free-radical polymerization
of a monomer composition M1) comprising at least one monomer A)
selected from .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids, salts of .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids, anhydrides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids and mixtures thereof, in the presence of at least one
polyether component PE) selected from polyetherols having a
number-average molecular weight of at least 200 g/mol, mono- and
di(C.sub.1-C.sub.6-alkyl) ethers of such polyetherols, surfactants
containing polyether groups, and mixtures thereof.
2. The multilayer film according to claim 1 comprising at least one
further layer comprising at least one polymer P2) selected from
natural and modified polysaccharides, homo- and copolymers
comprising repeat units which derive from vinyl alcohol, vinyl
esters, alkoxylated vinyl alcohols or mixtures thereof, homo- and
copolymers comprising at least one copolymerized monomer selected
from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole,
2-vinylpyridine, 4-vinylpyridine, salts of the three latter
monomers, vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridium
halides and mixtures thereof, homo- and copolymers of acrylic acid
and/or methacrylic acid, and at least one copolymerized maleic
monomer selected from maleic acid, maleic anhydride, maleic salts
and mixtures thereof, copolymers comprising at least one
copolymerized (meth)acrylic monomer selected from acrylic acid,
methacrylic acid, salts thereof and mixtures thereof and at least
one copolymerized hydrophobic monomer selected from
C.sub.1-C.sub.8-alkyl esters of (meth)acrylic acid,
C.sub.2-C.sub.10 olefins, styrene and .alpha.-methylstyrene,
copolymers comprising at least one copolymerized maleic monomer
selected from maleic acid, maleic anhydride, maleic salts and
mixtures thereof and at least one copolymerized C.sub.2-C.sub.8
olefin, homo- and copolymers of acrylamide and/or methacrylamide,
polyamino acids, water-soluble or water-dispersible polyamides,
polyalkylene glycols, mono- or diethers of polyalkylene glycols,
and mixtures thereof.
3. The multilayer film according to claim 2, wherein the polymer
P2) is selected from cellulose ethers and cellulose esters, homo-
and copolymers comprising repeat units which derive from vinyl
alcohol, vinyl esters, alkoxylated vinyl alcohols or mixtures
thereof, polymers selected from polyvinylpyrrolidone homopolymers,
polyvinylimidazole homopolymers, copolymers comprising
copolymerized vinylpyrrolidone and vinylimidazole,
polyvinylpyridine N-oxide, poly-N-carboxymethyl-4-vinylpyridium
halides, and mixtures thereof.
4. The multilayer film according to claim 2, wherein the polymer
P2) is selected from cellulose derivatives and mixtures of two or
more cellulose derivatives.
5. The multilayer film according to claim 1, wherein the monomer
composition M1) comprises, in addition to the at least one monomer
A), at least one monomer B) selected from olefinically unsaturated
sulfonic acids, salts of olefinically unsaturated sulfonic acids,
olefinically unsaturated phosphonic acids, salts of olefinically
unsaturated phosphonic acids and mixtures thereof.
6. The multilayer film according to claim 1, wherein the monomer
composition M1) additionally comprises at least one comonomer C)
selected from C1) nitrogen heterocycles having a free-radically
polymerizable .alpha.,.beta.-ethylenically unsaturated double bond,
C2) compounds of general formulae (I.a) and (I.b) ##STR00007## in
which the sequence of the alkylene oxide units is arbitrary, x is
0, 1 or 2, k and l are independently an integer from 0 to 100,
wherein a sum of k and l is at least 2, R.sup.1 is hydrogen or
C.sub.1-C.sub.8-alkyl, R.sup.2 is hydrogen, C.sub.1-C.sub.30-alkyl,
C.sub.2-C.sub.30-alkenyl or C.sub.5-C.sub.8-cycloalkyl, and X is O
or a group of a formula NR.sup.3 in which R.sup.3 is H, alkyl,
alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; C3)
vinylaromatics, C4) unsaturated hydrocarbons selected from
C.sub.2-C.sub.10 monoolefins and nonaromatic hydrocarbons having at
least two conjugated double bonds, C5) esters of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.1-C.sub.30-alkanols, C6) compounds having one
free-radically polymerizable .alpha.,.beta.-ethylenically
unsaturated double bond and at least one cationogenic and/or
cationic group per molecule, C7) esters of vinyl alcohol or allyl
alcohol with C.sub.1-C.sub.30-monocarboxylic acids, C8) esters of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.2-C.sub.30-alkanediols, and amides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.2-C.sub.30 amino alcohols having a primary or
secondary amino group, C9) monomers containing amide groups other
than I.a, C6) and C8); C10) .alpha.,.beta.-ethylenically
unsaturated nitriles, C11) vinyl halides, vinylidene halides, C12)
ethylenically unsaturated monomers having urea groups, and mixtures
of two or more than two of the aforementioned monomers C1) to
C12).
7. The multilayer film according to claim 1, wherein the monomer
composition M1) comprises acrylic acid and optionally at least one
comonomer selected from .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids other than acrylic acid, salts,
anhydrides, esters and amides of such .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids other than acrylic acid,
olefinically unsaturated sulfonic acids, salts of olefinically
unsaturated sulfonic acids, nitrogen heterocycles having a
free-radically polymerizable .alpha.,.beta.-ethylenically
unsaturated double bond, C.sub.2-C.sub.10 monoolefins, nonaromatic
hydrocarbons having at least two conjugated double bonds, vinyl
aromatics, N-vinyllactams and mixtures thereof.
8. The multilayer film according to claim 1, wherein the monomer
composition M1) comprises acrylic acid and at least one comonomer
selected from isobutene, diisobutene, methacrylic acid,
2-acrylamido-2-methylpropanesulfonic acid, maleic acid, maleic
anhydride, itaconic acid, N-vinylpyrrolidone, N-vinylcaprolactam,
N-vinylimidazole, styrene and mixtures thereof.
9. The multilayer film according to claim 1, wherein the monomer
composition M1), based on a total weight, comprises less than 0.1%
by weight of crosslinking monomers having two or more than two
free-radically polymerizable .alpha.,.beta.-ethylenically
unsaturated double bonds per molecule.
10. The multilayer film according to claim 1, wherein the monomer
composition M1) does not comprise any crosslinking monomers having
two or more than two free-radically polymerizable
.alpha.,.beta.-ethylenically unsaturated double bonds per
molecule.
11. The multilayer film according to claim 1, wherein the monomer
composition M1) consists to an extent of at least 80% by weight
based on a total weight of the monomer composition M1), of acrylic
acid.
12. The multilayer film according to claim 1, wherein the polyether
component PE) comprises at least one polyetherol having a
number-average molecular weight in a range from about 200 to 100
000 g/mol or a mono- or di-(C.sub.1-C.sub.2-alkyl) ether
thereof.
13. The multilayer film according to claim 1, wherein the polyether
component PE) comprises at least one polyetherol or one mono- or
di-(C1-C2-alkyl) ether thereof incorporating exclusively ethylene
oxide units as alkylene oxide units.
14. The multilayer film according to claim 1, wherein the polyether
component PE) comprises at least one surfactant containing
polyether groups, selected from alkyl polyoxyalkylene ethers, aryl
polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers,
alkoxylated animal and/or vegetable fats and/or oils, fatty amine
alkoxylates, fatty acid amide alkoxylates, fatty acid
diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid
esters, alkyl polyether sulfates, aryl polyether sulfates,
alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl
polyether sulfonates, alkylaryl polyether sulfonates, alkyl
polyether phosphates, aryl polyether phosphates, alkylaryl
polyether phosphates, glyceryl ether sulfonates, glyceryl ether
sulfates, monoglyceride (ether) sulfates, fatty acid amide ether
sulfates, polyoxyalkylene sorbitan fatty acid esters and mixtures
thereof.
15. The multilayer film according to claim 1, wherein the polyether
component PE) comprises at least one surfactant containing
polyether groups, selected from: alkyl polyoxyalkylene ethers of a
general formula (VI)
R.sup.10--O--(CH.sub.2CH.sub.2O).sub.x--(CHR.sup.11CH.sub.2O).sub.y-
--R.sup.2 (VI) in which R.sup.10 is a linear or branched alkyl
radical having 8 to 22 carbon atoms, R.sup.11 and R.sup.12 are
independently hydrogen or a linear or branched alkyl radical having
1 to 10 carbon atoms, and x and y are independently 0 to 300,
wherein a sum of x and y is >0; and surfactants which contain
hydroxyl groups and are of a general formula (VII)
R.sup.13--O--(CH.sub.2CH.sub.2O).sub.s--(CH.sub.2CH.sub.2CH.sub.2O).sub.t-
--(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O).sub.u--(CH.sub.2CHR.sup.14O).sub.v---
CH.sub.2CH(OH)R.sup.15 (VII) wherein the sequence of the alkylene
oxide units in the compounds of the formula (VII) is arbitrary, s,
t, u and v are independently an integer from 0 to 500, wherein a
sum of s, t, u and v is >0, R.sup.13 and R.sup.15 are
independently a straight-chain or branched saturated
C.sub.1-C.sub.40-alkyl radical or a mono- or polyunsaturated
C.sub.2-C.sub.40-alkenyl radical, and R.sup.14 is selected from
methyl, ethyl, n-propyl, isopropyl and n-butyl; fatty alcohol
polyoxyalkylene esters of a general formula (VIII)
R.sup.16--O--(CH.sub.2CH.sub.2O).sub.p--(CH.sub.2CHR.sup.17O).sub.q--C(.d-
bd.O)R.sup.18 (VIII) wherein the sequence of the alkylene oxide
units in the compounds of the formula (VIII) is arbitrary, p and q
are independently an integer from 0 to 500, wherein a sum of p and
q is >0, R.sup.16 and R.sup.18 are independently a
straight-chain or branched saturated C.sub.1-C.sub.40-alkyl radical
or a mono- or polyunsaturated C.sub.2-C.sub.40-alkenyl radical, and
R.sup.17 is selected from methyl, ethyl, n-propyl, isopropyl and
n-butyl.
16. The multilayer film according to claim 1, wherein at least one
of the layers comprises at least one additive and/or at least one
additive is present between at least two layers.
17. A process for producing a multilayer film as defined in claim
1, in which a1) a first free-flowing composition capable of film
formation is applied to a carrier material to obtain a first layer,
a2) the first layer applied to the carrier material is optionally
subjected to an increase in viscosity, a3) a second free-flowing
composition capable of film formation is applied to the first layer
obtained in step a1) or in step a2) to obtain a second layer, a4)
the second layer is optionally subjected to an increase in
viscosity, a5) step a3) is optionally repeated with a further
composition capable of film formation to obtain a further layer and
step a4) is optionally then repeated, it being possible to repeat
steps a3) and a4) once or more than once, a6) the layers applied to
the carrier material are optionally subjected to a further increase
in viscosity, a7) the multilayer film obtained is optionally
detached from the carrier material, with the proviso that the
free-flowing compositions each comprise a component which is
capable of film formation and is independently selected from at
least one polymer composition P1), at least one polymer P2) or a
mixture thereof, and with the proviso that at least one of the
free-flowing compositions and/or the carrier material comprises the
polymer composition P1) as defined in claim 1.
18. A method of using a multilayer film as defined in claim 1, the
method comprising using the multilayer film as a washing and
cleaning composition, for at least partial coating or ensheathing
of washing and cleaning compositions, as a dishwashing composition
or as a rinse aid, for at least partial coating or ensheathing of
dishwashing compositions or for at least partial coating or
ensheathing of rinse aids, as hygiene products, for at least
partial coating or ensheathing of hygiene products, as
disinfectants, for at least partial coating or ensheathing of
disinfectants, for at least partial coating or ensheathing of
personal care compositions, for at least partial coating or
ensheathing of personal cleansing compositions, for at least
partial coating or ensheathing of cosmetic compositions, as
pharmaceutical compositions, for at least partial coating or
ensheathing of pharmaceutical compositions, as crop protection
compositions, for at least partial coating or ensheathing of crop
protection compositions, for at least partial coating or
ensheathing of bait traps, as food or animal feed packaging, as
wetting agents, for at least partial coating or ensheathing of
wetting agents, as packaging for textiles, as lamination films, or
in composite systems (laminates) such as composite glass.
19. A sheath or coating for a washing composition portion, cleaning
composition portion or dishwashing composition portion, comprising
a multilayer film as defined in claim 1.
20. A washing or cleaning composition comprising: A) at least one
sheath and/or coating comprising a washing- and cleaning-active
multilayer film as defined in claim 1, B) at least one surfactant,
C) optionally at least one builder, D) optionally at least one
bleach system, E) optionally at least one further additive, and F)
optionally water.
21. A dishwashing composition comprising: Ga) at least one sheath
and/or coating comprising a multilayer film as defined in claim 1,
Gb) optionally at least one complexing agent, Gc) at least one
builder and/or cobuilder, Gd) at least one nonionic surfactant, Ge)
optionally at least one component selected from bleaches, bleach
activators and bleach catalysts, Gf) optionally at least one
enzyme, Gg) optionally at least one further additive, and Gh)
optionally water.
Description
FIELD OF INVENTION
[0001] The present invention relates to a multilayer film
comprising at least one layer comprising or consisting of a polymer
composition obtainable by free-radical polymerization of a monomer
composition comprising at least one monomer A) selected from
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids, salts of .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids, anhydrides of .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids and mixtures thereof,
wherein the free-radical polymerization is effected in the presence
of at least one polyether component. The invention further relates
to a process for producing such a multilayer film, to various uses
of such a multilayer film and specifically to a sheath or coating
for a washing composition, cleaning composition or dishwashing
detergent portion comprising or consisting of such a multilayer
film, and to washing compositions, cleaning compositions or
dishwashing compositions comprising such a multilayer film.
BACKGROUND
[0002] It is known that water-soluble films of polyvinyl alcohol
can be used for packaging of washing and cleaning compositions in
liquid, gel and solid form as portions. The polyvinyl alcohol film
dissolves at the start of the washing and cleaning process and
releases the washing and cleaning compositions, and so they are
able to display their effect. The advantages of the washing and
cleaning compositions packaged as portions (called single dose
units or mono dose units) for the consumer are manifold. These
include the avoidance of incorrect dosages, ease of handling, and
the fact that the consumer does not come into physical contact with
the constituents of the washing and cleaning compositions. These
additionally also include aesthetic aspects which lead to a
preference for the washing and cleaning compositions packaged as
portions. Current dosage forms can comprise a large number of
separately formulated active ingredients and auxiliaries which are
released individually in the cleaning process. Such multichamber
systems permit, for example, the separation of incompatible
constituents and hence the creation of new formulation concepts.
The proportion of the polyvinyl alcohol film in the total weight of
the washing or cleaning composition portion (single dose unit) is
between 2% and 20% by weight, according to the application.
[0003] One disadvantage of the polyvinyl alcohol films is that they
merely serve as packaging material and make no contribution at all
to the washing and cleaning performance. There is quite generally a
need for polymer films which do not just release particular
constituents but themselves make an active contribution.
Specifically, there is a need for washing- and cleaning-active
polymer films.
[0004] Lev Bromberg describes, in the Journal of Physical Chemistry
B (1998), 102, 11, 1956-1963, a material with thermoreversible gel
formation, the production of which involves polymerizing acrylic
acid in the presence of a PEO-PPO-PEO block copolymer. The reaction
proceeds in the absence of external solvents in order to achieve a
high proportion of branching and crosslinking in the resultant
products. These are neither water-soluble nor transparent. Possible
fields of use mentioned for these polymers are only very generally
pharmacy and food supplements (p. 1956, left-hand column,
"Introduction").
[0005] Lev Bromberg describes, in Ind. Eng. Chem. Res. 1998, 37,
4267-4274, polyether-modified polyacrylic acids, specifically by
polymerization of partly neutralized acrylic acid in the presence
of a PEO-PPO-PEO block copolymer.
[0006] WO 2005/012378 describes aqueous dispersions of
water-soluble polymers of anionic monomers and the use thereof as
thickeners for aqueous systems. For preparation thereof, anionic
monomers are polymerized in the presence of two water-soluble
polymers from different classes, which can also include
polyalkylene glycols. Example 4 (page 19, lines 14-27) relates to
the polymerization of acrylic acid in the presence of two different
polypropylene glycols and of maltodextrin. The dispersions are used
inter alia in personal care products, and in washing and cleaning
compositions. There is no description of use in the form of
films.
[0007] WO 2015/000969 describes the use of a polymer composition in
gel form, obtainable by a process in which [0008] a) a monomer
composition M1) is provided, consisting of [0009] A) at least one
.alpha.,.beta.-ethylenically unsaturated acid and [0010] B) 0% to
0.1% by weight, based on the total weight of the monomer
composition M1), of crosslinking monomers having two or more than
two polymerizable .alpha.,.beta.-ethylenically unsaturated double
bonds per molecule, [0011] b) the monomer composition M1) provided
in step a) is subjected to a free-radical polymerization in the
presence of at least one polyether component PE) selected from
polyetherols having a number-average molecular weight of at least
200 g/mol and the mono- and di(C.sub.1-C.sub.6-alkyl) ethers
thereof, surfactants containing polyether groups, and mixtures
thereof, in formulations for machine dishwashing. Again, there is
no description of use in the form of films.
[0012] WO 2015/000971 describes the use of a polymer composition in
gel form as described in WO 2015/000969 for further uses, but not
in the form of films.
[0013] WO 2015/000970 describes a process for producing a solid
polymer composition, especially in the form of a film or in the
form of a solid coating on a substrate or in particle form, in
which [0014] a) a monomer composition M1) is provided, comprising
[0015] A) at least one .alpha.,.beta.-ethylenically unsaturated
carboxylic acid, and [0016] B) less than 0.1% by weight, based on
the total weight of the monomer composition M1), of crosslinking
monomers having two or more than two polymerizable
.alpha.,.beta.-ethylenically unsaturated double bonds per molecule,
and [0017] b) the monomer composition M1) provided in step a) is
subjected to a free-radical polymerization in the presence of at
least one polyether component PE) selected from polyetherols having
a number-average molecular weight of at least 200 g/mol and the
mono- and di(C.sub.1-C.sub.6-alkyl) ethers thereof, surfactants
containing polyether groups, and mixtures thereof.
[0018] WO 01/00781 describes an active ingredient portion pack
comprising at least one washing-, cleaning- or dishwashing-active
preparation and an envelope fully or partly enveloping the
washing-, cleaning- or dishwashing-active preparation, in which the
envelope is soluble under washing, cleaning or dishwashing
conditions and comprises at least one individual component of the
washing-, cleaning- or dishwashing-active preparation in bound
form. It is not stated that the material of the envelope itself
actively participates in the washing or cleaning operation.
[0019] Unpublished European patent application 16160745.2 relates
to a monolaminar washing- and cleaning-active polymer film,
comprising or consisting of a polymer composition P1) obtainable by
free-radical polymerization of a monomer composition M1) comprising
at least one monomer A) selected from .alpha.,.beta.-ethylenically
unsaturated carboxylic acids, salts of .alpha.,.beta.-ethylenically
unsaturated carboxylic acids and mixtures thereof, in the presence
of at least one (C.sub.8-C.sub.18-alkyl)polyoxyalkylene ether
having an average of 3 to 12 alkylene oxide units per molecule.
Also described are a process for producing such a washing- and
cleaning-active polymer film, the use of such a polymer film and a
sheath or coating for a washing or cleaning composition portion
comprising or consisting of such a polymer film. There is no
description of multilaminar polymer films.
[0020] US 2011/0301070 describes a water-soluble strip comprising a
carrier in film form, at least one active ingredient and at least
one agent selected from heat-generating agents and breakdown
accelerators. The carrier in film form comprises a water-soluble
polymer which makes the carrier capable of dissolving in water and
in so doing releasing the active ingredient(s). The active
ingredients and agents may be applied to or incorporated into the
carrier in film form. Suitable water-soluble polymers mentioned are
a multitude of different acrylate polymers, polyvinyl alcohols and
polysaccharides. The water-soluble strip may be fully or partly
provided with a removable protective coating in order to protect it
from oxygen and/or water prior to use thereof.
[0021] EP 0 957 158 A1 describes a sheetlike article for washing,
comprising a thin layer of a phosphate-free, surfactant-containing
detergent composition having water-soluble sheets on both surfaces.
The water-soluble sheets may comprise water-soluble films or
textiles composed of water-soluble polymer fibers. Suitable
water-soluble polymers mentioned include polyvinyl alcohols,
polyvinylpyrrolidones, pullulan, polyacrylamides, poly(meth)acrylic
acids, polyethylene oxides, carboxymethyl cellulose and
hydroxyalkyl celluloses.
[0022] It is known that multilayer films having a layer
construction composed of at least two film laminas can be
provided.
[0023] WO 2010/069553 describes a multilayer film comprising an at
least flushable thermoplastic layer construction composed of [0024]
A) at least one layer which can at least be broken up by the action
of water and is resistant to cold water or can be dissolved
relatively slowly therein, based on at least one at least partly
hydrolyzed polyvinyl acetate, and [0025] B) at least one cold
water-soluble layer based on at least one at least partly
hydrolyzed polyvinyl acetate and at least one water
solubility-enhancing substance selected from the group comprising
biodegradable polymers, surfactants, inorganic pigments and
fillers.
[0026] A flushable layer construction is understood to mean that
resulting packages do not cause blockages in drains in the event of
flushing with water, for example a toilet flush. They serve as
protective packaging for a wide variety of different goods, such as
washing compositions or dishwashing compositions packaged in
individual portions (for example in the form of tabs), and for
hygiene articles such as tampons or sanitary napkins which are used
together with the flushable packaging. After the removal of the
packaging for use of these articles, the packaging can be disposed
of by simply flushing it away with the aid of a toilet flush.
[0027] U.S. Pat. No. 7,727,946 describes a process for producing
functionalized films for cleaning products, wherein a water-soluble
film bears a coating of a composition that exerts a particular
function. For this purpose, an aqueous solution of a functional
material is applied stepwise on at least one side of the
water-soluble film, in order to produce a multilayer coating on the
film. For this purpose, each layer applied is allowed to at least
partly dry before the next layer is applied. Each layer may
comprise different functional materials with cleaning properties,
barrier properties and/or solubility-modifying properties. In
addition, the aqueous solution comprises an agent that temporarily
reduces the solubility of the water-soluble film, such that it is
wetted but does not dissolve or swell. The individual layers are
preferably applied by a printing method such as flexographic
printing. Suitable film-forming polymers mentioned are polyvinyl
alcohols, polyvinylpyrrolidones, polyalkylene oxides,
polyacrylamides, polyacrylic acids, cellulose, cellulose ethers,
cellulose esters, cellulose amides, polyvinyl acetates,
polycarboxylic acids and salts thereof, polyamino acids,
polyamides, polyacrylamides, maleic/acrylic acid copolymers,
polysaccharides and mixtures thereof. Particular preference is
given to using polyvinyl alcohol films commercially available under
the Monosol M8630 name. Agents used that temporarily reduce the
solubility of the water-soluble film are salts such as sodium
sulfate, sodium citrate, etc. There is no description of
application of the functional materials together with film-forming
polymers. What is described, however, is application of a further
film-forming polymer, for example a polyvinyl alcohol, after the
application of the last layer of the functional materials.
[0028] It is an object of the present invention to provide a
multilayer film having at least one functional layer, especially at
least one layer having dispersing, film-inhibiting, emulsifying
and/or surfactant properties. This functional layer should
simultaneously be water-soluble. The other layers should stabilize
this functional layer and/or have functional properties of their
own. For applications in which the water solubility of the
multilayer film is of critical importance, it should be
water-soluble under the use conditions intended.
[0029] For use in washing, cleaning and dishwashing applications,
the multilayer film should have at least one of the following
properties: [0030] At least one layer of the multilayer film is to
include a film-forming polymer composition which has dispersing,
film-inhibiting, emulsifying and/or surfactant properties and hence
contributes to the washing and cleaning performance. [0031] Said
layer is to be compatible with a maximum number of different
constituents of washing, cleaning and dishwashing compositions.
[0032] Said layer is to be suitable for production of
storage-stable formulations. The multilayer film is to have
adequate stability both with respect to external effects, for
example air or air humidity, and with respect to internal effects,
for example the embedded or ensheathed constituents. Furthermore,
the constituents embedded into the multilayer film and/or
ensheathed by the multilayer film are also to be stabilized against
any loss of their properties. [0033] It is to be possible for at
least one layer of the multilayer film to comprise at least one
constituent which is released in the course of the washing,
cleaning or dishwashing operation. This constituent preferably
comprises water-soluble or water-dispersible constituents. This
release is preferably to be effected in a controlled manner and
especially in a particular phase of the washing or cleaning
operation. [0034] The multilayer film of the invention is also to
be suitable as a sheath or part of the sheath of a washing
composition portion, cleaning composition portion or dishwashing
composition portion. It is to be possible for the ensheathed
constituents to be released in the washing, cleaning or dishwashing
operation. This release is preferably also to be effected in a
controlled manner and especially in a particular phase of the
washing or cleaning operation. [0035] The multilayer films are to
be suitable for production of a multitude of different
formulations. It is firstly to be possible for the multilayer films
as such already to constitute the end product. In addition, it is
to be possible for the multilayer film to be an integral
constituent of a complex formulation. This may comprise, for
example, bags such as pouches (liquid tabs) or compressed shaped
bodies such as tablets ("tabs"), blocks, briquettes, or
multichamber systems, etc.
[0036] It has now been found that, surprisingly, it is possible to
provide multilayer films having advantageous physicochemical
properties and/or having use properties tailored to the respective
end use when they comprise at least one layer comprising or
consisting of a polymer composition obtainable by free-radical
polymerization of a monomer composition comprising at least one
monomer selected from .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids, salts of .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids, anhydrides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids and mixtures thereof, wherein the free-radical polymerization
is effected in the presence of at least one polyether
component.
SUMMARY OF THE INVENTION
[0037] The invention firstly provides a multilayer film comprising
at least one layer comprising or consisting of a polymer
composition P1) obtainable by free-radical polymerization of a
monomer composition M1) comprising at least one monomer A) selected
from .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids, salts of .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids, anhydrides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids and mixtures thereof, in the presence of at least one
polyether component PE) selected from polyetherols having a
number-average molecular weight of at least 200 g/mol, mono- and
di(C.sub.1-C.sub.6-alkyl) ethers of such polyetherols, surfactants
containing polyether groups, and mixtures thereof.
[0038] In a preferred embodiment, the multilayer film is produced
by a process in which at least one free-flowing composition capable
of film formation is applied to a carrier material, wherein the
carrier material and/or the at least one free-flowing composition
comprises or consists of a polymer composition P1) as defined above
and hereinafter.
[0039] The invention further provides a process for producing a
multilayer film as defined above and hereinafter, in which [0040]
a1) a first free-flowing composition capable of film formation is
applied to a carrier material to obtain a first layer, [0041] a2)
the first layer applied to the carrier material is optionally
subjected to an increase in viscosity, [0042] a3) a second
free-flowing composition capable of film formation is applied to
the first layer obtained in step a1) or in step a2) to obtain a
second layer, [0043] a4) the second layer is optionally subjected
to an increase in viscosity, [0044] a5) step a3) is optionally
repeated with a further composition capable of film formation to
obtain a further layer and step a4) is optionally then repeated, it
being possible to repeat steps a3) and a4) once or more than once,
[0045] a6) the layers applied to the carrier material are
optionally subjected to a further increase in viscosity, [0046] a7)
the multilayer film obtained is optionally detached from the
carrier material,
[0047] with the proviso that the free-flowing compositions each
comprise a component which is capable of film formation and is
independently selected from at least one polymer composition P1),
at least one polymer P2) or a mixture thereof, and with the proviso
that at least one of the free-flowing compositions and/or the
carrier material comprises or consists of a polymer composition P1)
as defined above and hereinafter.
[0048] The multilayer film can also be produced by a lamination
method. Laminating involves bonding two or more layers of the
multilayer film to one another over their area. If the multilayer
film is produced exclusively by lamination, all layers of the
multilayer film are bonded to one another over their area. The
lamination can be effected successively (layer by layer), or
laminates already consisting of two or more layers are bonded to
one another.
[0049] The multilayer film can also be produced by a wet-on-wet
application method. In addition, the multilayer film can be
produced using combinations of the aforementioned production
methods.
[0050] A polymer composition P1) as defined above and hereinafter
is preferably produced by [0051] A) providing a monomer composition
M1) comprising at least one monomer A) selected from
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids, salts of .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids, anhydrides of .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids and mixtures thereof,
[0052] B) subjecting the monomer composition M1) provided in step
A) to a free-radical polymerization in the presence of at least one
polyether component PE) selected from polyetherols having a
number-average molecular weight of at least 200 g/mol, mono- and
di(C.sub.1-C.sub.6-alkyl) ethers thereof, surfactants containing
polyether groups and mixtures thereof, optionally in the presence
of at least one additive.
[0053] If the polymer composition obtained in step B) comprises
anhydride functions, these can if desired be subjected to a partial
or complete hydrolysis, and/or, if the polymer composition obtained
in step B) comprises acid functions, these can if desired be
subjected to partial or complete neutralization.
[0054] The invention further provides for the use of a multilayer
film as defined above and hereinafter or obtainable by a process as
defined above and hereinafter as a washing and cleaning
composition, [0055] for at least partial coating or ensheathing of
washing and cleaning compositions, [0056] as a dishwashing
detergent or as a rinse aid, [0057] for at least partial coating or
ensheathing of dishwashing detergents or for at least partial
coating or ensheathing of rinse aids, [0058] as hygiene products,
[0059] for at least partial coating or ensheathing of hygiene
products, [0060] as disinfectants, [0061] for at least partial
coating or ensheathing of disinfectants, [0062] for at least
partial coating or ensheathing of personal care compositions,
[0063] for at least partial coating or ensheathing of personal
cleansing compositions, [0064] for at least partial coating or
ensheathing of cosmetic compositions, [0065] as pharmaceutical
compositions, [0066] for at least partial coating or ensheathing of
pharmaceutical compositions, [0067] as crop protection
compositions, [0068] for at least partial coating or ensheathing of
crop protection compositions, [0069] in bait traps, [0070] for at
least partial coating or ensheathing of bait traps, [0071] as food
or animal feed packaging, [0072] as wetting agents, [0073] for at
least partial coating or ensheathing of wetting agents, [0074] as
packaging for textiles, [0075] as lamination films, [0076] in
composite systems (laminates) such as composite glass.
[0077] A specific embodiment of the invention is the use of a
multilayer film as defined above and hereinafter, or obtainable by
a process as defined above and hereinafter, as washing composition
or as cleaning composition or as dishwashing composition.
[0078] A further specific embodiment of the invention is the use of
a multilayer film as defined above and hereinafter, or obtainable
by a process as defined above and hereinafter, for at least partial
ensheathing of a liquid or solid washing, cleaning or dishwashing
composition.
[0079] The invention further provides a sheath or coating for a
washing composition portion, cleaning composition portion or
dishwashing composition portion, comprising or consisting of a
multilayer film as defined above and hereinafter, or obtainable by
a process as defined above and hereinafter.
[0080] The invention further provides a washing or cleaning
composition comprising: [0081] A) at least one sheath and/or
coating comprising or consisting of a multilayer film as defined
above and hereinafter or obtainable by a process as defined above
and hereinafter, [0082] B) at least one surfactant, [0083] C)
optionally at least one builder, [0084] D) optionally at least one
bleach system, [0085] E) optionally at least one further additive,
preferably selected from enzymes, enzyme stabilizers, bases,
corrosion inhibitors, defoamers and foam inhibitors, dyes,
fragrances, fillers, tableting aids, disintegrants, thickeners,
solubilizers, organic solvents, electrolytes, pH modifiers, perfume
carriers, bitter substances, fluorescers, hydrotropes,
antiredeposition agents, optical brighteners, graying inhibitors,
antishrink agents, anticrease agents, dye transfer inhibitors,
antimicrobial active ingredients, antioxidants, anti-yellowing
agents, corrosion inhibitors, antistats, ironing aids,
hydrophobizing and impregnating agents, antiswell and antislip
agents and UV absorbers, and [0086] F) optionally water.
[0087] The invention further provides a dishwashing composition
comprising: [0088] Ga) at least one sheath and/or coating
comprising or consisting of a multilayer film of the invention,
[0089] Gb) optionally at least one complexing agent, [0090] Gc) at
least one builder and/or cobuilder, [0091] Gd) at least one
nonionic surfactant, [0092] Ge) optionally at least one component
selected from bleaches, bleach activators and bleach catalysts,
[0093] Gf) optionally at least one enzyme, [0094] Gg) optionally at
least one further additive, preferably selected from anionic or
zwitterionic surfactants, alkali carriers, polymeric dispersants,
corrosion inhibitors, defoamers and foam inhibitors, dyes,
fragrances, bitter substances, fillers, tablet disintegrants,
organic solvents, tableting aids, disintegrants, thickeners and
solubilizers, [0095] Gh) optionally water.
DETAILED DESCRIPTION OF THE INVENTION
[0096] A "multilayer film" in the context of the invention is
understood to mean a film composite where at least two films are
permanently and fully bonded over a significant portion of their
area. This is understood to mean that at least two films are
permanently and fully bonded over at least 50% of their area. When
two films of different size are bonded to one another, at least the
film having the smaller area is permanently and fully bonded over
at least 50% of its area. Thus, the multilayer films of the
invention differ from known films for washing and cleaning
composition portions where an individual film or 2 or more films
are joined to one another by at least one weld seam. The latter
films are permanently and fully bonded to one another over at most
10% of their area.
[0097] The term "multilayer film" in the context of the present
invention refers to a self-supporting flat structure having at
least two film layers. The maximum thickness of the multilayer
films of the invention is preferably at most 30 mm, more preferably
at most 20 mm, especially at most 15 mm. It will be apparent that
the maximum thickness of the multilayer films of the invention
depends on their field of use. Multilayer films for ensheathing or
coating for a washing composition portion, cleaning composition
portion or dishwashing composition portion preferably have a
thickness of not more than 1500 .mu.m, more preferably not more
than 1000 .mu.m. Multilayer films which themselves serve as washing
compositions or as cleaning compositions or as dishwashing
compositions preferably have a thickness of not more than 30 mm,
more preferably not more than 20 mm.
[0098] Moreover, the thickness of the multilayer films of the
invention is small in relation to the length and width. Preferably,
the thickness of the multilayer films is smaller by a factor of at
least 2, more preferably of at least 5 and especially of at least
10 than the length of the greatest longitudinal axis. In a specific
embodiment, the thickness of the multilayer films is smaller by a
factor of at least 20, more specifically at least 50, even more
specifically at least 100 and very specifically at least 500 than
the length of the greatest longitudinal axis. In principle, the
upper value for the greatest longitudinal extent of the multilayer
films of the invention is uncritical. The multilayer films of the
invention can be produced, for example, in the form of film rolls,
where the greatest length may even be in the region of 100 m or
higher.
[0099] The multilayer films of the invention have an essentially
two-dimensional extent. The length and/or width of the film is
generally at least 5 mm and preferably at least 10 mm. The maximum
length and/or width of the film is generally uncritical and may be
in the millimeter, centimeter or meter range according to the field
of application.
[0100] The multilayer films of the invention and those produced by
the process of the invention are suitable as such for use as
washing, cleaning and dishwashing compositions. For this purpose,
individual components of a washing, cleaning or dishwashing
composition or else a complete washing, cleaning or dishwashing
composition may be formulated in the form of a multilayer film. A
washing, cleaning or dishwashing composition in the form of a
multilayer film dissolves at the start and/or in the course of the
respective use (for example in the washing or rinse water), thus
releases the constituents of the washing, cleaning and dishwashing
composition and, in dissolved form, because of the dispersing,
film-inhibiting, emulsifying and surfactant properties of the
polymer composition P1) present and of any further active layers,
contributes considerably to the washing and cleaning
performance.
[0101] The multilayer films of the invention or those produced by
the process of the invention are also suitable for packaging of
washing, cleaning and dishwashing compositions in liquid, gel and
solid form as portions. They dissolve at the start and/or in the
course of the respective use (for example in the washing or rinse
water), thus release the constituents of the washing, cleaning and
dishwashing composition and, in dissolved form, because of the
polymer composition P1) present and any further active layers,
contribute considerably to the washing and cleaning performance. In
the field of washing and cleaning compositions, the multilayer
films serve to achieve dispersing, film-inhibiting, emulsifying and
surfactant properties. In the field of dishwashing compositions and
especially of automatic dishwashing (ADW), the multilayer films
additionally serve to improve the rinse aid performance and the
drying process.
[0102] In the context of the present invention, the terms "washing
composition portion", "cleaning composition portion" and
"dishwashing composition portion" are understood to mean an amount
of a washing composition or cleaning composition or dishwashing
composition sufficient for a washing, cleaning or dishwashing
operation that takes place in an aqueous phase. This may, for
example, be a machine washing operation as conducted with
commercial washing machines. This may, for example, also be a
machine dishwashing operation as conducted with commercial machine
dishwashers and referred to as "automatic dishwashing" (ADW).
According to the invention, this term is also understood to mean an
active ingredient portion for a manual washing operation or a
manually conducted cleaning or dishwashing operation (as conducted,
for example, in a handwash basin, a sink or a bowl). The multilayer
films of the invention are preferably used for production of active
ingredient portions for machine washing, cleaning or dishwashing
operations.
[0103] In the context of this application, some compounds which can
be derived either from acrylic acid or from methacrylic acid or
from mixtures of the two are referred to by insertion of the
"(meth)" syllable into the compound derived from acrylic acid.
[0104] The organic radicals of the variables mentioned above and
below constitute an individual enumeration of individual group
members. The prefix C.sub.n-C.sub.m denotes the possible number of
carbon atoms in the respective group.
[0105] If the term "alkyl" is used without a prefix
(C.sub.n-C.sub.m), it represents a linear or (over and above 3
carbon atoms) branched saturated aliphatic radical having generally
1 to 40 carbon atoms ("C.sub.1-C.sub.40-alkyl"), preferably 1 to 30
carbon atoms ("C.sub.1-C.sub.30-alkyl").
[0106] In the context of the present invention,
C.sub.1-C.sub.4-alkyl is a linear or branched alkyl radical having
1 to 4 carbon atoms. Examples of C.sub.1-C.sub.4-alkyls are methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and
tert-butyl.
[0107] C.sub.1-C.sub.7-alkyl is a linear or branched alkyl radical
having 1 to 7 carbon atoms. Examples of C.sub.1-C.sub.7-alkyl are,
in addition to those mentioned for C.sub.1-C.sub.4-alkyl, pentyl,
1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,
1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl,
1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,
1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,
2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,
1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,
1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,
1-ethyl-2-methylpropyl, heptyl and the constitutional isomers
thereof.
[0108] C.sub.1-C.sub.8-alkyl is a linear or branched alkyl radical
having 1 to 8 carbon atoms. Examples of C.sub.1-C.sub.8-alkyl are,
in addition to those mentioned for C.sub.1-C.sub.7-alkyl, octyl,
2-ethylhexyl and the constitutional isomers thereof.
[0109] C.sub.1-C.sub.10-alkyl is a linear or branched alkyl radical
having 1 to 10 carbon atoms. Examples of C.sub.1-C.sub.10-alkyl
are, in addition to those mentioned for C.sub.1-C.sub.8-alkyl,
nonyl, decyl, 2-propylheptyl and the constitutional isomers
thereof.
[0110] C.sub.1-C.sub.20-alkyl is a linear or branched alkyl radical
having 1 to 20 carbon atoms. Examples of C.sub.1-C.sub.20-alkyl
are, in addition to those mentioned for C.sub.1-C.sub.10-alkyl,
undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
heptadecyl, octadecyl, nonadecyl, eicosyl and the constitutional
isomers thereof.
[0111] C.sub.1-C.sub.30-alkyl is a linear or branched alkyl radical
having 1 to 30 carbon atoms. Examples of C.sub.1-C.sub.30-alkyl
are, in addition to those mentioned for C.sub.1-C.sub.20-alkyl,
heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,
heptacosyl, octacosyl, nonacosyl, triacontyl and the constitutional
isomers thereof.
[0112] C.sub.1-C.sub.40-alkyl is a linear or branched alkyl radical
having 1 to 40 carbon atoms. Examples of C.sub.1-C.sub.40-alkyl
are, in addition to those mentioned for C.sub.1-C.sub.30-alkyl, the
higher homologs having 31 to 40 carbon atoms. Examples of
C.sub.8-C.sub.22-alkyl are octyl, 2-ethylhexyl and the
constitutional isomers thereof.
[0113] C.sub.8-C.sub.18-alkyl is a linear or branched alkyl radical
having 8 to 18 carbon atoms. Suitable C.sub.8-C.sub.18-alkyls are
octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,
tetracosyl and the constitutional isomers thereof. In a preferred
embodiment, they are predominantly linear C.sub.8-C.sub.18-alkyl
radicals, as also occur in natural or synthetic fatty alcohols, and
oxo process alcohols.
[0114] C.sub.12-C.sub.18-alkyl is a linear or branched alkyl
radical having 12 to 18 carbon atoms. Suitable
C.sub.12-C.sub.18-alkyls are dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,
heneicosyl, docosyl, tricosyl, tetracosyl and the constitutional
isomers thereof. In a preferred embodiment, they are predominantly
linear C.sub.12-C.sub.18-alkyl radicals, as also occur in natural
or synthetic fatty alcohols, and oxo process alcohols.
[0115] In the context of the present application, the expression
C.sub.9-C.sub.11 alcohols represents a mixture comprising alcohols
having 9 carbon atoms and alcohols having 11 carbon atoms.
C.sub.12-C.sub.14 alcohols are a mixture comprising alcohols having
12 carbon atoms and alcohols having 14 carbon atoms.
C.sub.13-C.sub.15 alcohols are a mixture comprising alcohols having
13 carbon atoms and alcohols having 15 carbon atoms.
C.sub.12-C.sub.18 alcohols are a mixture comprising alcohols having
12 carbon atoms, alcohols having 14 carbon atoms, alcohols having
16 carbon atoms and alcohols having 18 carbon atoms.
[0116] If the term "alkenyl" is used without a prefix
(C.sub.n-C.sub.m), it represents a linear or branched
monounsaturated (i.e. comprising one C--C double bond) aliphatic
radical having generally 2 to 40 carbon atoms
("C.sub.2-C.sub.40-alkenyl"), preferably 2 to 30 carbon atoms
("C.sub.2-C.sub.30-alkenyl").
[0117] Examples of C.sub.2-C.sub.3-alkenyl are ethenyl, 1-propenyl,
2-propenyl or 1-methylethenyl. Examples of C.sub.2-C.sub.4-alkenyl
are, in addition to those mentioned for C.sub.2-C.sub.3-alkenyl,
1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,
2-methyl-1-propenyl, 1-methyl-2-propenyl or 2-methyl-2-propenyl.
Examples of C.sub.2-C.sub.6-alkenyl are, in addition to those
mentioned for C.sub.2-C.sub.4-alkenyl, 1-pentenyl, 2-pentenyl,
3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,
3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,
1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl,
1-ethyl-2-methyl-2-propenyl and the like. Examples of
C.sub.2-C.sub.10-alkenyl are, in addition to those mentioned for
C.sub.2-C.sub.6-alkenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl,
1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1-nonenyl, 2-nonenyl,
3-nonenyl, 4-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, 4-decenyl,
5-decenyl and the like.
[0118] If the term "cycloalkyl" is used without a prefix
(C.sub.n-C.sub.m), it represents a saturated monocyclic
cycloaliphatic radical having generally 3 to 10 carbon atoms
("C.sub.3-C.sub.10-cycloalkyl"), preferably 3 to 8 carbon atoms
("C.sub.3-C.sub.8-cycloalkyl"), and of course does not have any
heteroatoms as ring members (i.e. all ring members are carbon
atoms).
[0119] Examples of C.sub.3-C.sub.4-cycloalkyl are cyclopropyl and
cyclobutyl. Examples of C.sub.3-C.sub.5-cycloalkyl are cyclopropyl,
cyclobutyl and cyclopentyl. Examples of C.sub.3-C.sub.6-cycloalkyl
are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples
of C.sub.3-C.sub.7-cycloalkyl are cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl and cycloheptyl. Examples of
C.sub.3-C.sub.8-cycloalkyl are cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of
C.sub.3-C.sub.10-cycloalkyl are cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and
cyclodecyl.
[0120] "Aryl" is a mono-, bi- or polycyclic carbocyclic aromatic
radical without heteroatoms as ring members. A monocyclic aromatic
radical is phenyl. In bicyclic aryl radicals, two aromatic rings
are fused to one another; in other words, they share two adjacent
carbon atoms as ring members. Examples of bicyclic aryl groups are
1- and 2-naphthyl. In polycyclic aryl groups, three or more rings
are fused. Examples of polycyclic aryl groups are phenanthrenyl,
anthracenyl, tetracenyl, 1H-benzo[a]phenalenyl, pyrenyl and the
like. In the context of the present application, the term "aryl"
also encompasses bi- or polycyclic radicals in which not all rings
are aromatic; it is a prerequisite that at least one ring is
aromatic. Examples of these are indanyl, indenyl, tetralinyl,
6,7,8,9-tetra-hydro-5H-benzo[7]annulenyl, fluorenyl,
9,10-dihydroanthracenyl, 9,10-dihydro-phenanthrenyl,
1H-benzo[a]phenalenyl and the like. The aryl group has generally 6
to 30, especially 6 to 20 and specifically 6 to 10 carbon atoms as
ring members.
[0121] If the term "heterocycloalkyl" is used without a prefix
(C.sub.n-C.sub.m) and without specification of the ring
heteroatoms, it represents a saturated monocyclic heterocyclic
radical having generally 3 to 8 ring members and at least one
heteroatom and/or heteroatom-containing group, preferably 1, 2, 3
or 4 heteroatoms and/or heteroatom-containing groups, as ring
members. The heteroatom and the heteroatom-containing group are
selected from N, O, S, NO, SO and SO.sub.2.
[0122] Examples of these are oxiran-2-yl, thiiran-2-yl,
aziridin-1-yl, aziridin-2-yl, oxetan-2-yl, oxetan-3-yl,
thietan-2-yl, thietan-3-yl, 1-oxothietan-2-yl, 1-oxothietan-3-yl,
1,1-dioxothietan-2-yl, 1,1-dioxothietan-3-yl, azetidin-1-yl,
azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl,
tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl,
1-oxotetrahydrothien-2-yl, 1,1-dioxotetrahydrothien-2-yl,
1-oxotetrahydrothien-3-yl, 1,1-dioxotetrahydrothien-3-yl,
pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl,
pyrazolidin-1-yl, pyrazolidin-3-yl, pyrazolidin-4-yl,
pyrazolidin-5-yl, imidazolidin-1-yl, imidazolidin-2-yl,
imidazolidin-4-yl, oxazolidin-2-yl, oxazolidin-3-yl,
oxazolidin-4-yl, oxazolidin-5-yl, isoxazolidin-2-yl,
isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-5-yl,
thiazolidin-2-yl, thiazolidin-3-yl, thiazolidin-4-yl,
thiazolidin-5-yl, isothiazolidin-2-yl, isothiazolidin-3-yl,
isothiazolidin-4-yl, isothiazolidin-5-yl, 1,2,4-oxadiazolidin-2-yl,
1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-4-yl,
1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-2-yl,
1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-4-yl,
1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-1-yl,
1,2,4-triazolidin-3-yl, 1,2,4-triazolidin-4-yl,
1,3,4-oxadiazolidin-2-yl, 1,3,4-oxadiazolidin-3-yl,
1,3,4-thiadiazolidin-2-yl, 1,3,4-thiadiazolidin-3-yl,
1,3,4-triazolidin-1-yl, 1,3,4-triazolidin-2-yl,
1,3,4-triazolidin-3-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl,
tetrahydropyran-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl,
1,3-dioxan-5-yl, 1,4-dioxan-2-yl, piperidin-1-yl, piperidin-2-yl,
piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-1-yl,
hexahydropyridazin-3-yl, hexahydropyridazin-4-yl,
hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl,
hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl,
piperazin-2-yl, 1,3,5-hexahydrotriazin-1-yl,
1,3,5-hexahydrotriazin-2-yl, 1,2,4-hexahydrotriazin-1-yl,
1,2,4-hexahydrotriazin-2-yl, 1,2,4-hexahydrotriazin-3-yl,
1,2,4-hexahydrotriazin-4-yl, 1,2,4-hexahydrotriazin-5-yl,
1,2,4-hexahydrotriazin-6-yl, morpholin-2-yl, morpholin-3-yl,
morpholin-4-yl, thiomorpholin-2-yl, thiomorpholin-3-yl,
thiomorpholin-4-yl, 1-oxothiomorpholin-2-yl,
1-oxothiomorpholin-3-yl, 1-oxothio-morpholin-4-yl,
1,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl,
1,1-dioxothiomorpholin-4-yl, azepan-1-, -2-, -3- or -4-yl,
oxepan-2-, -3-, -4- or -5-yl, hexahydro-1,3-diazepinyl,
hexahydro-1,4-diazepinyl, hexahydro-1,3-oxazepinyl,
hexahydro-1,4-oxazepinyl, hexahydro-1,3-dioxepinyl,
hexahydro-1,4-dioxepinyl, oxocanyl, thiocanyl, azocanyl,
[1,3]diazocanyl, [1,4]diazocanyl, [1,5]diazocanyl, [1,5]oxazocanyl
and the like.
[0123] If the term "heteroaryl" or "hetaryl" is used without a
prefix (C.sub.n-C.sub.m) and without specification of the ring
heteroatoms, it represents an aromatic monocyclic heterocyclic
radical having 5 or 6 ring members and at least one heteroatom
and/or heteroatom-containing group, preferably 1, 2, 3 or 4
heteroatoms and/or heteroatom-containing groups, as ring members.
The heteroatom and the heteroatom-containing group are selected
from N, O, S, NO, SO and SO.sub.2.
[0124] Examples of these are 2-furyl, 3-furyl, 2-thienyl,
3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl,
3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl,
4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl,
3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl,
5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl,
1,3,4-triazol-1-yl, 1,3,4-triazol-2-yl, 1,3,4-triazol-3-yl,
1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl,
1,2,5-oxadiazol-3-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl,
1,3,4-oxadiazol-2-yl, 1,2,5-thiadiazol-3-yl, 1,2,3-thiadiazol-4-yl,
1,2,3-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 2-pyridinyl,
3-pyridinyl, 4-pyridinyl, 1-oxopyridin-2-yl, 1-oxo-pyridin-3-yl,
1-oxopyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl,
4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl,
1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,3,4-tetrazin-1-yl,
1,2,3,4-tetrazin-2-yl, 1,2,3,4-tetrazin-5-yl and the like.
[0125] Monoolefins are alkenes; in other words, they are linear or
branched aliphatic monounsaturated hydrocarbons having only one
C--C double bond. If the term is used without a prefix
(C.sub.n-C.sub.m), it represents a linear or branched
monounsaturated (i.e. comprising one C--C double bond) aliphatic
hydrocarbon having generally 2 to 40 carbon atoms
("C.sub.2-C.sub.40 monoolefin" or "C.sub.2-C.sub.40-alkene"),
preferably 2 to 30 carbon atoms ("C.sub.2-C.sub.30 monoolefin" or
"C.sub.2-C.sub.3-alkene"), especially 2 to 10 carbon atoms
("C.sub.2-C.sub.10 monoolefin" or "C.sub.2-C.sub.30-alkene").
Examples of C.sub.2-C.sub.10 monoolefins are ethene, propene,
but-1-ene, but-2-ene, isobutene, pent-1-ene, pent-2-ene,
2-methyl-but-1-ene, 2-methyl-but-2-ene, 3-methyl-but-1-ene,
3-methyl-but-2-ene, 2,2-dimethylprop-1-ene, hex-1-ene, hex-2-ene,
hex-3-ene, hept-1-ene, hept-2-ene, hept-3-ene, oct-1-ene,
oct-2-ene, oct-3-ene, oct-4-ene, non-1-ene, non-2-ene, non-3-ene,
non-4-ene, dec-1-ene, dec-2-ene, dec-3-ene, dec-4-ene, dec-5-ene
and the positional isomers thereof.
[0126] Nonaromatic hydrocarbons having at least two conjugated
double bonds refer to both aliphatic and cycloaliphatic unsaturated
hydrocarbons having at least two conjugated double bonds. The
cycloaliphatic unsaturated hydrocarbons having at least two
conjugated double bonds are either those which do not comprise the
maximum number of conjugated C--C double bonds defined by the ring
size or those which do comprise the maximum number of conjugated
C--C double bonds defined by the ring size but do not satisfy the
Huckel rule, whether because the molecule is homoaromatic,
antiaromatic or a nonaromatic polyene.
[0127] Aliphatic hydrocarbons having at least two conjugated double
bonds generally comprise 4 to 20 carbon atoms. Examples of
aliphatic hydrocarbons having at least two conjugated double bonds
are 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene,
1,3,5-hexatriene, 1,3-heptadiene, 2,4-heptadiene,
1,3,4-heptatriene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene,
1,3,5-octatriene, 2,4,6-octatriene, 1,3,5,7-octatetraene and the
like.
[0128] Cycloaliphatic hydrocarbons having at least two conjugated
double bonds generally comprise 4 to 20 carbon atoms as ring
members. Examples are 1,3-cyclopentadiene, 1,3-cyclohexadiene,
1,3-cycloheptadiene, 1,3,5-cycloheptatriene, 1,3-cyclooctadiene,
1,3,5-cyclooctatriene, 1,3,5,7-cyclooctatetraene and the like.
[0129] Alkanols are monohydroxyalkanes, i.e. compounds R--OH in
which R is a linear or branched alkyl radical as defined above. If
the term is used without a prefix (C.sub.n-C.sub.m), it represents
a C.sub.1-C.sub.30-alkanol. Examples of C.sub.1-C.sub.3-alkanols
are methanol, ethanol, n-propanol and isopropanol. Examples of
C.sub.1-C.sub.4-alkanols are, in addition to those mentioned for
the C.sub.1-C.sub.3-alkanols, n-butanol, sec-butanol, isobutanol
and tert-butanol. Examples of C.sub.1-C.sub.20-alkanols are, in
addition to those mentioned for the C.sub.1-C.sub.4-alkanols,
pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol,
decanol, 2-propylheptanol, undecanol, lauryl alcohol, tridecanol,
myristyl alcohol, pentadecanol, palmityl alcohol, heptadecanol,
stearyl alcohol, nonadecanol, eicosanol and the positional and
constitutional isomers thereof. Examples of
C.sub.1-C.sub.30-alkanols are, in addition to those mentioned for
C.sub.1-C.sub.20-alkanols, the higher homologs having 21 to 30
carbon atoms and the positional and constitutional isomers
thereof.
[0130] Alkanediols are dihydroxyalkanes, i.e. alkanes in which two
hydrogen atoms have been replaced by OH groups, where at least two
carbon atoms must be between the two hydroxyl groups (i.e. hydrates
are not encompassed by this term). If the term is used without a
prefix (C.sub.n-C.sub.m), it represents a
C.sub.2-C.sub.30-alkanediol. Examples of
C.sub.2-C.sub.3-alkanediols are ethylene glycol (ethane-1,2-diol),
propane-1,2-diol and propane-1,3-diol. Examples of
C.sub.2-C.sub.4-alkanediols are, in addition to those mentioned for
the C.sub.2-C.sub.3-alkanediols, butane-1,2-diol, butane-1,3-diol
and butane-1,4-diol. Examples of C.sub.2-C.sub.6-alkanediols are,
in addition to those mentioned for the C.sub.2-C.sub.4-alkanediols,
pentane-1,5-diol and hexane-1,6-diol. Examples of
C.sub.2-C.sub.20-alkanediols are, in addition to those mentioned
for the C.sub.2-C.sub.6-alkanediols, heptane-1,7-diol,
octane-1,8-diol, nonane-1,9-diol, decane-1,10-diol,
undecane-1,11-diol, dodecane-1,12-diol, tridecane-1,13-diol,
tetradecane-1,14-diol, pentadecane-1,15-diol, hexadecane-1,16-diol,
heptadecane-1,17-diol, octadecane-1,18-diol, nonadecane-1,19-diol,
eicosane-1,20-diol. Examples of C.sub.2-C.sub.30-alkanediols are,
in addition to those mentioned for C.sub.2-C.sub.20-alkanediols,
the higher homologs having 21 to 30 carbon atoms.
[0131] In the context of the present application, the expression
C.sub.9-C.sub.11 alcohols represents a mixture comprising alcohols
having 9 carbon atoms and alcohols having 11 carbon atoms.
C.sub.12-C.sub.14 alcohols are a mixture comprising alcohols having
12 carbon atoms and alcohols having 14 carbon atoms.
C.sub.13-C.sub.15 alcohols are a mixture comprising alcohols having
13 carbon atoms and alcohols having 15 carbon atoms.
C.sub.12-C.sub.18 alcohols are a mixture comprising alcohols having
12 carbon atoms, alcohols having 14 carbon atoms, alcohols having
16 carbon atoms and alcohols having 18 carbon atoms.
[0132] Polymer Composition P1)
[0133] The polymer composition P1) is prepared by free-radical
polymerization of the monomer composition M1) in the presence of at
least one polyether component PE). This affords specific polymer
compositions P1) having advantageous properties. Without being
bound to a theory, hydrogen bonds are able to form between the
growing polymer and the polyether component, and these influence
the properties of the resultant polymer composition. Thus, polymer
compositions P1) having a high content of the polyether component
can be attained; these cannot be prepared by mixing the separately
prepared polymer with the polyether component. Free-radical polymer
degradation advantageously does not take place here.
[0134] For production of the multilayer films of the invention,
preference is given to using polymer compositions P1) having a low
glass transition temperature TG. Preferably, the polymer
compositions P1) used for production of the multilayer films of the
invention have a glass transition temperature TG in the range from
0 to 80.degree. C., preferably from 0 to 60.degree. C., especially
from 0 to 30.degree. C.
[0135] The glass transition temperatures (Tg) described in the
context of this application can be determined by means of
differential scanning calorimetry (DSC).
[0136] In a preferred embodiment, the polymer compositions P1) used
for production of the washing- and cleaning-active polymer films of
the invention take the form of a transparent film.
[0137] Monomer Composition M1)
[0138] Monomer A)
[0139] The monomer composition M1) used for production of the
polymer composition P1) comprises at least one monomer A) selected
from .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids, salts of .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids, anhydrides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids and mixtures thereof.
[0140] In a specific embodiment, the monomer composition M1)
consists solely of .alpha.,.beta.-ethylenically unsaturated
carboxylic acids, salts of .alpha.,.beta.-ethylenically unsaturated
carboxylic acids and mixtures thereof.
[0141] The .alpha.,.beta.-ethylenically unsaturated carboxylic acid
is preferably selected from acrylic acid, methacrylic acid,
ethacrylic acid, maleic acid, fumaric acid, itaconic acid,
.alpha.-chloroacrylic acid, crotonic acid, citraconic acid,
mesaconic acid, glutaconic acid and aconitic acid. Suitable salts
of the aforementioned acids are especially the sodium, potassium
and ammonium salts, and the salts with amines. The monomers A) can
be used as such or as mixtures with one another. The stated
proportions by weight all refer to the acid form.
[0142] Preferably, the at least one .alpha.,.beta.-ethylenically
unsaturated carboxylic acid is used for polymerization in
non-neutralized form. If the .alpha.,.beta.-ethylenically
unsaturated carboxylic acids are used for polymerization in partly
neutralized form, the acid groups are neutralized preferably to an
extent of at most 50 mol %, particularly preferably to an extent of
at most 30 mol %. The partial or full neutralization can also be
effected during the polymerization or after the polymerization has
ended.
[0143] Suitable bases for neutralization of the
.alpha.,.beta.-ethylenically unsaturated carboxylic acids, and also
the unsaturated sulfonic acids and phosphonic acids mentioned
hereinafter, are alkali metal hydroxides such as NaOH and KOH,
alkaline earth metal hydroxides such as Ca(OH).sub.2 and
Mg(OH).sub.2, ammonia and amine bases. Preferred amines are
alkanolamines such as ethanolamine, diethanolamine and
triethanolamine. If desired, partial or full neutralization of the
acid groups may also follow after the polymerization.
[0144] More preferably, monomer A) is selected from acrylic acid,
methacrylic acid, maleic acid, fumaric acid, itaconic acid, salts
of the aforementioned carboxylic acids and mixtures thereof.
[0145] More particularly, monomer A) is selected from acrylic acid,
methacrylic acid, salts of acrylic acid, salts of methacrylic acid
and mixtures thereof.
[0146] In a specific embodiment, exclusively acrylic acid is used
as monomer A).
[0147] Monomer A) is used preferably in an amount of 50% to 100% by
weight, more preferably 60% to 100% by weight, based on the total
weight of the monomer composition M1).
[0148] In a preferred embodiment, the monomer composition M1)
consists to an extent of at least 50% by weight, preferably to an
extent of at least 80% by weight and especially to an extent of at
least 90% by weight, based on the total weight of the monomer
composition M1), of acrylic acid and/or acrylic acid salts.
[0149] Monomer B)
[0150] The monomer composition M1) may, in addition to the monomers
A), comprise at least one monomer B) selected from unsaturated
sulfonic acids, salts of unsaturated sulfonic acids, unsaturated
phosphonic acid, salts of unsaturated phosphonic acids and mixtures
thereof.
[0151] Monomer B) is preferably selected from
2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid,
allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate,
sulfopropyl acrylate, sulfopropyl methacrylate,
2-hydroxy-3-acryloyloxypropylsulfonic acid,
2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic
acid, vinylphosphonic acid, allylphosphonic acid, salts of the
aforementioned acids and mixtures thereof.
[0152] A preferred monomer B) is
2-acrylamido-2-methylpropanesulfonic acid.
[0153] Suitable salts of the aforementioned acids are especially
the sodium, potassium and ammonium salts, and the salts with
amines. The monomers B) can be used as such or as mixtures with one
another. The stated proportions by weight all refer to the acid
form.
[0154] Preferably, the monomer composition M1) in that case
consists to an extent of at least 50% by weight, more preferably to
an extent of at least 80% by weight and especially to an extent of
at least 90% by weight, based on the total weight of the monomer
composition M1), of monomers A) and B). When the monomer
composition M1) comprises at least one monomer B), it is preferably
used in an amount of 0.1% to 50% by weight, more preferably 1% to
25% by weight, based on the total weight of the monomer composition
M1).
[0155] Monomers C)
[0156] The monomer composition M1) may additionally comprise at
least one further monomer other than the monomers containing acid
groups and salts thereof (=monomer C).
[0157] The monomer composition M1) may thus have the following
monomer compositions: A) or A)+B) or A)+C) or A)+B)+C).
[0158] Preferably, the monomer composition M1) additionally
comprises at least one monomer C) selected from [0159] C1) nitrogen
heterocycles having a free-radically polymerizable
.alpha.,.beta.-ethylenically unsaturated double bond, [0160] C2)
compounds of the general formulae (I.a) and (I.b)
[0160] ##STR00001## [0161] in which [0162] the sequence of the
alkylene oxide units is arbitrary, [0163] x is 0, 1 or 2, [0164] k
and l are independently an integer from 0 to 100, where the sum of
k and l is at least 2, preferably at least 5, [0165] R.sup.1 is
hydrogen or C.sub.1-C.sub.8-alkyl, [0166] R.sup.2 is hydrogen,
C.sub.1-C.sub.30-alkyl, C.sub.2-C.sub.30-alkenyl or
C.sub.5-C.sub.8-cycloalkyl, and [0167] X is O or a group of the
formula NR.sup.3 in which R.sup.3 is H, alkyl, alkenyl, cycloalkyl,
heterocycloalkyl, aryl or hetaryl; [0168] C3) vinylaromatics,
[0169] C4) unsaturated hydrocarbons selected from C.sub.2-C.sub.10
monoolefins and nonaromatic hydrocarbons having at least two
conjugated double bonds, [0170] C5) esters of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.1-C.sub.30-alkanols, [0171] C6) compounds having
one free-radically polymerizable .alpha.,.beta.-ethylenically
unsaturated double bond and at least one cationogenic and/or
cationic group per molecule, [0172] C7) esters of vinyl alcohol or
allyl alcohol with C.sub.1-C.sub.30-monocarboxylic acids, [0173]
C8) esters of .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids with C.sub.2-C.sub.30-alkanediols, amides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.2-C.sub.30 amino alcohols having a primary or
secondary amino group, [0174] C9) monomers containing amide groups
other than I.a), C6) and C8); [0175] C10)
.alpha.,.beta.-ethylenically unsaturated nitriles, [0176] C11)
vinyl halides, vinylidene halides, [0177] C12) ethylenically
unsaturated monomers having urea groups, and mixtures of two or
more than two of the aforementioned monomers C1) to C12).
[0178] Monomer C1)
[0179] Preferred nitrogen heterocycles with a free-radically
polymerizable .alpha.,.beta.-ethylenically unsaturated double bond
C1) are selected from N-vinylimidazole (1-vinylimidazole), vinyl-
and allyl-substituted nitrogen heterocycles other than
N-vinylimidazole, and mixtures thereof.
[0180] The amine nitrogens of the aforementioned compounds can be
used to produce charged cationic groups either by protonation with
acids or by quaternization with alkylating agents. Suitable
monomers C1) are also the compounds obtained by protonation or
quaternization of 1-vinylimidazole and different vinyl- and
allyl-substituted nitrogen heterocycles. Acids suitable for the
protonation are, for example, carboxylic acids such as lactic acid
or mineral acids such as phosphoric acid, sulfuric acid and
hydrochloric acid. Alkylating agents suitable for quaternization
are C.sub.1-C.sub.4-alkyl halides or diC.sub.1-C.sub.4-alkyl)
sulfates, such as ethyl chloride, ethyl bromide, methyl chloride,
methyl bromide, dimethyl sulfate and diethyl sulfate. A protonation
or quaternization may generally either precede or follow the
polymerization. Preferably, a protonation or quaternization follows
the polymerization. Examples of such charged monomers C1) are
quaternized vinylimidazoles, especially 3-methyl-1-vinylimidazolium
chloride, methosulfate and ethosulfate.
[0181] Preferred monomers C1) are also vinyl- and allyl-substituted
nitrogen heterocycles other than vinylimidazoles, selected from
2-vinylpyridine, 4-vinylpyridine, 2-allylpyridine, 4-allylpyridine,
2-vinylpiperidine, 4-vinylpiperidine and the salts thereof obtained
by protonation or by quaternization.
[0182] More particularly, the monomer composition M1) comprises at
least one comonomer C1) selected from 1-vinylimidazole,
2-vinylpyridine, 4-vinylpyridine, 2-allylpyridine, 4-allylpyridine
and the salts thereof obtained by protonation or by quaternization.
Specifically, the monomer composition M1) comprises
1-vinylimidazole as comonomer C1).
[0183] Monomer C2)
[0184] The monomer composition M1) may additionally comprise at
least one monomer C2) selected from compounds of the general
formulae (I.a) and (I.b), as defined above.
[0185] In the formulae I.a) and I.b), k is preferably an integer
from 1 to 500, more preferably 2 to 400, especially 3 to 250.
Preferably, l is an integer from 0 to 100.
[0186] Preferably, R.sup.1 in the formula I.a) is hydrogen, methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,
n-pentyl or n-hexyl, especially hydrogen, methyl or ethyl.
[0187] Preferably, R.sup.2 in the formulae I.a) and I.b) is
n-octyl, 1,1,3,3-tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl,
n-undecyl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl,
octadecyl, nonadecyl, arachinyl, behenyl, lignoceryl, cerotinyl,
melissyl, palmitoleyl, oleyl, linoleyl, linolenyl, stearyl,
lauryl.
[0188] Preferably, X in the formula I.a) is O or NH, especially
O.
[0189] More preferably, the monomer composition M1) comprises at
least one monomer C2) selected from compounds of the general
formulae (I.a1) and (I.b1)
##STR00002##
[0190] in which [0191] the sequence of the alkylene oxide units is
arbitrary, [0192] x is 0, 1 or 2, [0193] k and l are independently
an integer from 0 to 100, where the sum of k and l is at least 2,
preferably at least 5, [0194] R.sup.1 is hydrogen or methyl, [0195]
R.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl.
[0196] In the formulae I.a1) and I.b1), k is preferably an integer
from 1 to 100, more preferably 2 to 50, especially 3 to 30.
Preferably, l is an integer from 0 to 50.
[0197] Preferably, R.sup.2 in the formulae I.a1) and I.b1) is
hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or
tert-butyl.
[0198] In the formula I.b1), x is preferably 1 or 2.
[0199] Suitable polyether acrylates I.a) or I.a1) are, for example,
the polycondensation products of the aforementioned
.alpha.,.beta.-ethylenically unsaturated mono- and/or dicarboxylic
acids and the acid chlorides, acid amides and acid anhydrides
thereof with polyetherols. Suitable polyetherols can be prepared
easily by reacting ethylene oxide, propylene 1,2-oxide and/or
epichlorohydrin with a starter molecule such as water or a
short-chain alcohol R.sup.2--OH. The alkylene oxides can be used
individually, alternately in succession, or as a mixture. The
polyether acrylates I.a1) can be used alone or in mixtures to
prepare the polymers used in accordance with the invention.
[0200] Suitable allyl alcohol alkoxylates I.b) or I.b1) are, for
example, the etherification products of allyl chloride with
appropriate polyetherols. Suitable polyetherols can be prepared
easily by reacting ethylene oxide, propylene 1,2-oxide and/or
epichlorohydrin with a starter alcohol R.sup.2--OH. The alkylene
oxides can be used individually, alternately in succession, or as a
mixture. The allyl alcohol alkoxylates I.b) can be used alone or in
mixtures to prepare the polymers used in accordance with the
invention.
[0201] Monomers C2) used are especially methyl diglycol acrylate,
methyl diglycol methacrylate, ethyl diglycol acrylate or ethyl
diglycol methacrylate. Preference is given to ethyl diglycol
acrylate.
[0202] Monomer C3)
[0203] The monomer composition M1) may additionally comprise at
least one monomer C3) selected from vinylaromatics. Preferred
vinylaromatics C3) are styrene, 2-methylstyrene, 4-methylstyrene,
2-(n-butyl)styrene, 4-(n-butyl)styrene, 4-(n-decyl)styrene and
mixtures thereof. Particular preference is given to styrene and
2-methylstyrene, especially styrene.
[0204] Monomer C4)
[0205] The monomer composition M1) may additionally comprise at
least one unsaturated hydrocarbon C4) selected from
C.sub.2-C.sub.10 monoolefins and nonaromatic hydrocarbons having at
least two conjugated double bonds.
[0206] Examples of C.sub.2-C.sub.10 monoolefins are ethene,
propene, but-1-ene, but-2-ene, isobutene, pent-1-ene, pent-2-ene,
2-methyl-but-1-ene, 2-methyl-but-2-ene, 3-methyl-but-1-ene,
3-methyl-but-2-ene, 2,2-dimethylprop-1-ene, hex-1-ene, hex-2-ene,
hex-3-ene, hept-1-ene, hept-2-ene, hept-3-ene, oct-1-ene,
oct-2-ene, oct-3-ene, oct-4-ene, non-1-ene, non-2-ene, non-3-ene,
non-4-ene, dec-1-ene, dec-2-ene, dec-3-ene, dec-4-ene, dec-5-ene
and the positional isomers thereof, and also unsaturatedly
terminated oligomers and polymers of the abovementioned olefins,
especially of the .alpha.-olefins (ethene, propene, but-1-ene,
pent-1-ene, hex-1-ene, hept-1-ene, oct-1-ene, non-1-ene,
dec-1-ene).
[0207] Nonaromatic hydrocarbons having at least two conjugated
double bonds refer to both aliphatic and cycloaliphatic unsaturated
hydrocarbons having at least two conjugated double bonds. The
cycloaliphatic unsaturated hydrocarbons having at least two
conjugated double bonds are either those which do not comprise the
maximum number of conjugated C--C double bonds defined by the ring
size or those which do comprise the maximum number of conjugated
C--C double bonds defined by the ring size but do not satisfy the
Huckel rule, whether because the molecule is homoaromatic,
antiaromatic or a nonaromatic polyene.
[0208] Aliphatic hydrocarbons having at least two conjugated double
bonds generally comprise 4 to 20 carbon atoms. Examples of
aliphatic hydrocarbons having at least two conjugated double bonds
are 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene,
2,4-hexadiene, 1,3,5-hexatriene, 1,3-heptadiene, 2,4-heptadiene,
1,3,4-heptatriene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene,
1,3,5-octatriene, 2,4,6-octatriene, 1,3,5,7-octatetraene and the
like.
[0209] Cycloaliphatic hydrocarbons having at least two conjugated
double bonds generally comprise 4 to 20 carbon atoms as ring
members. Examples are 1,3-cyclopentadiene, 1,3-cyclohexadiene,
1,3-cycloheptadiene, 1,3,5-cycloheptatriene, 1,3-cyclooctadiene,
1,3,5-cyclooctatriene, 1,3,5,7-cyclooctatetraene and the like.
[0210] Preferred monomers C4) are ethene, propene, butene,
isobutene, diisobutene, isoprene, 1,3-butadiene and mixtures
thereof.
[0211] Monomer C5)
[0212] The monomer composition M1) may additionally comprise at
least one monomer C5) selected from esters of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.1-C.sub.30-alkanols.
[0213] Suitable esters of .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids with C.sub.1-C.sub.30-alkanols are,
for example, methyl (meth)acrylate, methyl ethacrylate, ethyl
(meth)acrylate, ethyl ethacrylate, n-propyl (meth)acrylate,
isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl
(meth)acrylate, tert-butyl ethacrylate, n-pentyl (meth)acrylate,
n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl
(meth)acrylate, 1,1,3,3-tetramethylbutyl (meth)acrylate, ethylhexyl
(meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate,
n-undecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl
(meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate,
heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, arachinyl
(meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate,
cerotinyl (meth)acrylate, melissyl (meth)acrylate, palmitoleyl
(meth)acrylate, oleyl (meth)acrylate, linoleyl (meth)acrylate,
linolenyl (meth)acrylate, stearyl (meth)acrylate, lauryl
(meth)acrylate and mixtures thereof.
[0214] Monomer C6)
[0215] The monomer composition M1) may additionally comprise at
least one monomer C6) selected from compounds having a
free-radically polymerizable .alpha.,.beta.-ethylenically
unsaturated double bond and at least one cationogenic and/or
cationic group per molecule.
[0216] The cationogenic and/or cationic groups of the monomers C6)
are preferably nitrogen-containing groups such as primary,
secondary and tertiary amino groups, and quaternary ammonium
groups. Preferably, the nitrogen-containing groups are tertiary
amino groups or quaternary ammonium groups. Charged cationic groups
can be produced from the amine nitrogens either by protonation or
by quaternization with acids or alkylating agents. Examples of
these include carboxylic acids such as lactic acid, or mineral
acids such as phosphoric acid, sulfuric acid and hydrochloric acid,
and examples of alkylating agents include C.sub.1-C.sub.4-alkyl
halides or sulfates, such as ethyl chloride, ethyl bromide, methyl
chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. A
protonation or quaternization may generally either precede or
follow the polymerization.
[0217] Preferably, the monomers C6) are selected from esters of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with amino alcohols which may be mono- or dialkylated on the
amine nitrogen, amides of .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids with diamines having at least one
primary or secondary amino group, N,N-diallylamine,
N,N-diallyl-N-alkylamines and derivatives thereof, and mixtures
thereof.
[0218] The esters of .alpha.,.beta.-ethylenically unsaturated mono-
and dicarboxylic acids with amino alcohols which may be mono- or
dialkylated on the amine nitrogen preferably derive from
C.sub.2-C.sub.12 amino alcohols mono- or
di-C.sub.1-C.sub.8-alkylated on the amine nitrogen. Suitable acid
components of these esters are, for example, acrylic acid,
methacrylic acid, fumaric acid, maleic acid, itaconic acid,
crotonic acid, maleic anhydride, monobutyl maleate and mixtures
thereof. The acid components used are preferably acrylic acid,
methacrylic acid and mixtures thereof.
[0219] Preferred monomers C6) are N-methylaminoethyl
(meth)acrylate, N-ethylaminoethyl (meth)acrylate,
N-(n-propyl)aminoethyl (meth)acrylate, N-(tert-butyl)aminoethyl
(meth)acrylate, N,N-dimethylaminomethyl (meth)acrylate,
N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminomethyl
(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate,
N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl
(meth)acrylate and N,N-dimethylaminocyclohexyl (meth)acrylate.
[0220] Suitable monomers C6) are additionally the amides of the
aforementioned .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids with diamines having at least one primary or
secondary amino group. Preference is given to diamines having one
tertiary amino group and one primary or secondary amino group.
[0221] Examples of preferred monomers C6) are
N-[tert-butylaminoethyl](meth)acrylamide,
N-[2-(dimethylamino)ethyl]acrylamide,
N-[2-(dimethylamino)ethyl]methacrylamide,
N-[3-(dimethylamino)propyl]acrylamide,
N-[3-(dimethylamino)propyl]methacrylamide,
N-[4-(dimethylamino)butyl]acrylamide,
N-[4-(dimethylamino)butyl]methacrylamide,
N-[2-(diethylamino)ethyl]acrylamide,
N-[4-(dimethylamino)cyclohexyl]acrylamide and
N-[4-(dimethylamino)cyclohexyl]methacrylamide.
[0222] Monomer C7)
[0223] The monomer composition M1) may additionally comprise at
least one monomer C7) selected from esters of vinyl alcohol or
allyl alcohol with C.sub.1-C.sub.30 monocarboxylic acids.
[0224] Suitable esters of vinyl alcohol with
C.sub.1-C.sub.30-monocarboxylic acids are, for example, the esters
of vinyl alcohol with C.sub.1-C.sub.30 monocarboxylic acids such as
acetic acid, propionic acid, n-butanoic acid, 2-methylpropanoic
acid, n-pentanoic acid, 2,2-dimethylpropanoic acid, n-hexanoic
acid, n-heptanoic acid, n-octanoic acid,
2,2,4,4-tetramethylpentanoic acid, 2-ethylhexanoic acid, n-nonanoic
acid, n-decanoic acid, n-undecanoic acid, tridecanoic acid,
myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic
acid, octadecanoic acid, nonadecanoic acid, arachic acid, behenic
acid, lignoceric acid, cerotic acid, melissic acid, palmitoleic
acid, oleic acid, linoleic acid, linolenic acid, stearic acid,
lauric acid.
[0225] Monomer C8)
[0226] The monomer composition M1) may additionally comprise at
least one monomer C8) selected from esters of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.2-C.sub.30-alkanediols and amides of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids with C.sub.2-C.sub.30 amino alcohols having a primary or
secondary amino group.
[0227] Suitable esters of .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids with C.sub.2-C.sub.30-alkanediols are
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,
3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate,
3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate,
4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate,
6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate,
3-hydroxy-2-ethylhexyl methacrylate, etc.
[0228] Suitable amides of .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids with C.sub.2-C.sub.30-amino alcohols
having a primary or secondary amino group are
2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide,
2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide,
2-hydroxypropylmethacrylamide, 3-hydroxypropylacrylamide,
3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide,
3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide,
4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide,
6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and
3-hydroxy-2-ethylhexylmethacrylamide.
[0229] Monomer C9)
[0230] The monomer composition M1) may additionally comprise at
least one monomer C9) selected from monomers containing amide
groups other than I.a, C6) and C8).
[0231] Suitable monomers C9) containing amide groups are compounds
of the general formula (V)
##STR00003##
[0232] where
[0233] one of the R.sup.6 to R.sup.8 radicals is a group of the
formula CH.sub.2.dbd.CR.sup.9-- where R.sup.9.dbd.H or
C.sub.1-C.sub.4-alkyl and the other R.sup.6 to R.sup.8 radicals are
each independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or
hetaryl,
[0234] where R.sup.6 and R.sup.7, together with the amide group to
which they are bonded, can also be a lactam having 5 to 8 ring
atoms,
[0235] where R.sup.7 and R.sup.8, together with the nitrogen atom
to which they are bonded, can also be a five- to seven-membered
heterocycle.
[0236] Preferably, the monomers C9) are selected from primary
amides of .alpha.,.beta.-ethylenically unsaturated monocarboxylic
acids, N-vinylamides of saturated monocarboxylic acids,
N-vinyllactams, N-alkyl- and N,N-dialkylamides of
.alpha.,.beta.-ethylenically unsaturated monocarboxylic acids and
mixtures thereof.
[0237] Preferred monomers C9) are N-vinyllactams and derivatives
thereof which may have, for example, one or more
C.sub.1-C.sub.6-alkyl substituents such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, tert-butyl, etc. These include, for
example, N-vinyl-pyrrolidone, N-vinylpiperidone,
N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone,
N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone,
N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam,
N-vinyl-7-ethyl-2-caprolactam, etc.
[0238] Particular preference is given to using N-vinylpyrrolidone
and/or N-vinylcaprolactam.
[0239] Suitable monomers C9) are also acrylamide and
methacrylamide.
[0240] Suitable N-alkyl- and N,N-dialkylamides of
.alpha.,.beta.-ethylenically unsaturated monocarboxylic acids are,
for example, methyl(meth)acrylamide, methylethacrylamide,
ethyl(meth)acrylamide, ethylethacrylamide,
n-propyl(meth)acrylamide, isopropyl(meth)acrylamide,
n-butyl(meth)acrylamide, tert-butyl(meth)acrylamide,
tert-butylethacrylamide, n-pentyl(meth)acrylamide,
n-hexyl(meth)acrylamide, n-heptyl(meth)acrylamide,
n-octyl(meth)acrylamide, 1,1,3,3-tetramethylbutyl(meth)acrylamide,
ethylhexyl(meth)acrylamide, n-nonyl(meth)acrylamide,
n-decyl(meth)acrylamide, n-undecyl(meth)acrylamide,
tridecyl(meth)acrylamide, myristyl(meth)acrylamide,
pentadecyl(meth)acrylamide, palmityl(meth)acrylamide,
heptadecyl(meth)acrylamide, nonadecyl(meth)acrylamide,
arachinyl(meth)acrylamide, behenyl(meth)acrylamide,
lignoceryl(meth)acrylamide, cerotyl(meth)acrylamide,
melissyl(meth)acrylamide, palmitoleyl(meth)acrylamide,
oleyl(meth)acrylamide, linoleyl(meth)acrylamide,
linolenyl(meth)acrylamide, stearyl(meth)acrylamide,
lauryl(meth)acrylamide, N-methyl-N-(n-octyl)(meth)acrylamide,
N,N-di(n-octyl)(meth)acrylamide and mixtures thereof.
[0241] Open-chain N-vinylamide compounds suitable as monomers C9)
are, for example, N-vinylformamide, N-vinyl-N-methylformamide,
N-vinylacetamide, N-vinyl-N-methylacetamide,
N-vinyl-N-ethylacetamide, N-vinylpropionamide,
N-vinyl-N-methylpropionamide, N-vinylbutyramide and mixtures
thereof. Preference is given to using N-vinylformamide.
[0242] Monomer C10)
[0243] The monomer composition M1) may additionally comprise at
least one monomer C10) selected from .alpha.,.beta.-ethylenically
unsaturated nitriles.
[0244] Suitable .alpha.,.beta.-ethylenically unsaturated nitriles
are acrylonitrile or methacrylonitrile.
[0245] Monomer C11)
[0246] The monomer composition M1) may additionally comprise at
least one monomer C11) selected from vinyl halides and vinylidene
halides.
[0247] Suitable vinyl halides and vinylidene halides are vinyl
chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride
and mixtures thereof.
[0248] Monomer C12)
[0249] The monomer composition M1) may additionally comprise at
least one monomer C12) selected from ethylenically unsaturated
monomers having urea groups.
[0250] Suitable monomers C12) having urea groups are N-vinylurea,
N-allylurea or derivatives of imidazolidin-2-one. These include
N-vinyl- and N-allylimidazolidin-2-one,
N-vinyloxy-ethylimidazolidin-2-one,
N-(2-(meth)acrylamidoethyl)imidazolidin-2-one, N-(2-(meth)
acryloyloxyethyl)imidazolidin-2-one (i.e. 2-ureido(meth)acrylate),
N-[2-((meth) acryloyloxyacetamido)ethyl]imidazolidin-2-one,
etc.
[0251] In a particular embodiment, the monomer composition M1)
comprises acrylic acid and optionally at least one comonomer
selected from .alpha.,.beta.-ethylenically unsaturated mono- and
dicarboxylic acids other than acrylic acid, salts, anhydrides,
esters and amides of such .alpha.,.beta.-ethylenically unsaturated
mono- and dicarboxylic acids other than acrylic acid, olefinically
unsaturated sulfonic acids, salts of olefinically unsaturated
sulfonic acids, nitrogen heterocycles having a free-radically
polymerizable .alpha.,.beta.-ethylenically unsaturated double bond,
C.sub.2-C.sub.10 monoolefins, nonaromatic hydrocarbons having at
least two conjugated double bonds, vinyl aromatics, N-vinyllactams
and mixtures thereof.
[0252] In a specific embodiment, the monomer composition M1)
comprises acrylic acid and optionally at least one comonomer
selected from isobutene, diisobutene, methacrylic acid,
2-acrylamido-2-methylpropanesulfonic acid, maleic acid, maleic
anhydride, itaconic acid, N-vinylpyrrolidone, N-vinylcaprolactam,
N-vinylimidazole, styrene and mixtures thereof.
[0253] In a very specific embodiment, the monomer composition M1)
comprises acrylic acid and optionally at least one comonomer
selected from methacrylic acid,
2-acrylamido-2-methylpropanesulfonic acid and mixtures thereof.
[0254] More particularly, the monomer composition M1) consists to
an extent of at least 80% by weight, preferably to an extent of at
least 90% by weight and especially to an extent of at least 95% by
weight, based on the total weight of the monomer composition M1),
of acrylic acid.
[0255] The monomer composition M1) may comprise each of the further
monomers C1) to [0256] C12) preferably in an amount of 0% to 30% by
weight, more preferably 0% to 20% by weight and especially 0% to
10% by weight, based on the total weight of the monomer composition
M1). When the monomer composition M1) comprises at least one
monomer selected from C1) to C12), it does so in each case
preferably in an amount of 0.1% to 30% by weight, more preferably
1% to 20% by weight and especially 1.5% to 10% by weight, based on
the total weight of the monomer composition M1).
[0257] In a specific embodiment, the monomer composition M1) does
not comprise any further comonomers except for the monomers A) and
B).
[0258] Even more specifically, the monomer composition M1) does not
comprise any further comonomers apart from acrylic acid.
[0259] The polymer composition P1) comprises essentially
uncrosslinked polymers. The monomer composition M1) used for
production of the polymer composition P1) of the invention thus
especially does not comprise any added crosslinking monomers. In
the context of the invention, crosslinking monomers are compounds
having two or more than two polymerizable ethylenically unsaturated
double bonds per molecule.
[0260] Preferably, the monomer composition M1), based on the total
weight, comprises less than 0.1% by weight, more preferably less
than 0.05% by weight and especially less than 0.001% by weight of
crosslinking monomers having two or more than two free-radically
polymerizable .alpha.,.beta.-ethylenically unsaturated double bonds
per molecule.
[0261] In a specific embodiment, the monomer composition M1) does
not comprise any crosslinking monomers having two or more than two
polymerizable .alpha.,.beta.-ethylenically unsaturated double bonds
per molecule.
[0262] Polyether Component PE)
[0263] Suitable polyether components PE) are polyetherols having a
number-average molecular weight of at least 200 g/mol and the mono-
and di(C.sub.1-C.sub.6-alkyl) ethers thereof.
[0264] Suitable polyetherols and the mono- and
di(C.sub.1-C.sub.6-alkyl) ethers thereof may be linear or branched,
preferably linear. Suitable polyetherols and the mono- and
di(C.sub.1-C.sub.6-alkyl) ethers thereof generally have a
number-average molecular weight in the range from about 200 to 100
000 g/mol, preferably 300 to 50 000 g/mol and more preferably 500
to 40 000 g/mol. Suitable polyetherols are, for example,
water-soluble or water-dispersible nonionic polymers having repeat
alkylene oxide units. Preferably, the proportion of repeat alkylene
oxide units is at least 30% by weight, based on the total weight of
the compound. Suitable polyetherols are polyalkylene glycols, such
as polyethylene glycols, polypropylene glycols,
polytetrahydrofurans and alkylene oxide copolymers. Suitable
alkylene oxides for preparation of alkylene oxide copolymers are,
for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2-
and 2,3-butylene oxide. Suitable examples are copolymers of
ethylene oxide and propylene oxide, copolymers of ethylene oxide
and butylene oxide, and copolymers of ethylene oxide, propylene
oxide and at least one butylene oxide. The alkylene oxide
copolymers may comprise the copolymerized alkylene oxide units in
randomly distributed form or in the form of blocks. Preferably, the
proportion of repeat units derived from ethylene oxide in the
ethylene oxide/propylene oxide copolymers is 40% to 99% by weight.
Particularly preferred polyether components PE) are ethylene oxide
homopolymers and ethylene oxide/propylene oxide copolymers.
[0265] Suitable polyether components PE) are additionally the mono-
and diC.sub.1-C.sub.2-alkyl) ethers of the above-described
polyetherols. Preference is given to polyalkylene glycol monomethyl
ethers and polyalkylene glycol dimethyl ethers.
[0266] Suitable polyether components PE) are additionally
surfactants containing polyether groups. In general, nonionic and
ionic surfactants having at least one nonpolar group and at least
one polar group and comprising a polyether group are suitable.
[0267] The surfactants PE) containing polyether groups are
preferably selected from alkyl polyoxyalkylene ethers, aryl
polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers,
alkoxylated animal and/or vegetable fats and/or oils, fatty amine
alkoxylates, fatty acid amide alkoxylates, fatty acid
diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid
esters, alkyl polyether sulfates, aryl polyether sulfates,
alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl
polyether sulfonates, alkylaryl polyether sulfonates, alkyl
polyether phosphates, aryl polyether phosphates, alkylaryl
polyether phosphates, glyceryl ether sulfonates, glyceryl ether
sulfates, monoglyceride (ether) sulfates, fatty acid amide ether
sulfates, polyoxyalkylene sorbitan fatty acid esters and mixtures
thereof.
[0268] The preferred nonionic surfactants PE) containing polyether
groups include, for example: [0269] alkyl polyoxyalkylene ethers
which derive from low molecular weight C.sub.3-C.sub.6 alcohols or
from C.sub.7-C.sub.30 fatty alcohols. The ether component here may
be derived from ethylene oxide units, propylene oxide units,
1,2-butylene oxide units, 1,4-butylene oxide units and random
copolymers and block copolymers thereof. [0270] Suitable nonionic
surfactants comprise, inter alia, surfactants of the general
formula (VI)
[0270]
R.sup.10--O--(CH.sub.2CH.sub.2O).sub.x--(CHR.sup.11CH.sub.2O).sub-
.y--R.sup.12 (VI) [0271] in which R.sup.10 is a linear or branched
alkyl radical having 6 to 22 carbon atoms, [0272] R.sup.11 and
R.sup.12 are each independently hydrogen or a linear or branched
alkyl radical having 1 to 10 carbon atoms or H, where R.sup.12 is
preferably methyl, and [0273] x and y are each independently 0 to
300. Preferably, x=1 to 100 and y=0 to 30. [0274] These especially
also include fatty alcohol alkoxylates and oxo alcohol alkoxylates,
such as isotridecyl alcohol polyoxyethylene ethers and oleyl
alcohol polyoxyethylene ethers. [0275] surfactants containing
hydroxyl groups of the general formula (VII)
[0275]
R.sup.13--O--(CH.sub.2CH.sub.2O).sub.s--(CH.sub.2CH.sub.2CH.sub.2-
O).sub.t--(CH.sub.2CH.sub.2CH.sub.2CH.sub.2O).sub.u--(CH.sub.2CHR.sup.14O)-
.sub.v--CH.sub.2CH(OH)R.sup.15 (VII) [0276] where [0277] the
sequence of the alkylene oxide units in the compounds of the
formula (VII) is arbitrary, [0278] s, t, u and v are each
independently an integer from 0 to 500, where the sum of s, t, u
and v is >0, [0279] R.sup.13 and R.sup.15 are each independently
a straight-chain or branched saturated C.sub.1-C.sub.40-alkyl
radical or a mono- or polyunsaturated C.sub.2-C.sub.40-alkenyl
radical, and [0280] R.sup.14 is selected from methyl, ethyl,
n-propyl, isopropyl and n-butyl.
[0281] In the compounds of the general formula (VII), the sum of s,
t, u and v is preferably a value of 10 to 300, more preferably of
15 to 200 and especially of 20 to 150.
[0282] Preferably, t and u are each 0. In that case, the sum of s
and v is preferably a value of 10 to 300, more preferably of 15 to
200 and especially of 20 to 150.
[0283] In the compounds of the general formula (VII), R.sup.13 and
R.sup.15 are preferably independently a straight-chain or branched
saturated C.sub.2-C.sub.30-alkyl radical. At the same time,
R.sup.13 and R.sup.15 may also be mixtures of different alkyl
radicals.
[0284] In the compounds of the general formula (VII), R.sup.14 is
preferably methyl or ethyl, especially methyl.
[0285] A preferred embodiment is surfactants containing hydroxyl
groups of the general formula (VII.1)
R.sup.13--O--(CH.sub.2CH.sub.2O).sub.s--(CH.sub.2CH(CH.sub.3)O).sub.v--C-
H.sub.2CH(OH)R.sup.15 (VII.1) [0286] where [0287] the sequence of
the --(CH.sub.2CH.sub.2O)-- and the (CH.sub.2CH(CH.sub.3)O)-- units
is arbitrary, [0288] s and v are each independently an integer from
0 to 500, where the sum of s and v is >0, and [0289] R.sup.13
and R.sup.15 are independently a straight-chain saturated
C.sub.1-C.sub.30-alkyl radical or a branched saturated
C.sub.3-C.sub.30-alkyl radical or a mono- or polyunsaturated
C.sub.2-C.sub.30-alkenyl radical.
[0290] In the compounds of the general formula (VII.1), the sum of
s and v is preferably a value of 10 to 300, more preferably of 15
to 200 and especially of 20 to 150.
[0291] The group of these nonionic surfactants includes, for
example, hydroxy mixed ethers of the general formula
(C.sub.6-22-alkyl)-CH(OH)CH.sub.2O-(EO).sub.20-120-(C.sub.2-26-alkyl).
[0292] alcohol polyoxyalkylene esters of the general formula
(VIII)
[0292]
R.sup.16--O--(CH.sub.2CH.sub.2O).sub.p--(CH.sub.2CHR.sup.17O).sub-
.q--C(.dbd.O)R.sup.18 (VIII) [0293] where [0294] the sequence of
the alkylene oxide units in the compounds of the formula (VIII) is
arbitrary, [0295] p and q are each independently an integer from 0
to 500, where the sum of p and q is >0, [0296] R.sup.16 and
R.sup.18 are each independently a straight-chain or branched
saturated C.sub.1-C.sub.40-alkyl radical or a mono- or
polyunsaturated C.sub.2-C.sub.40-alkenyl radical, and [0297]
R.sup.17 is selected from methyl, ethyl, n-propyl, isopropyl and
n-butyl.
[0298] In the compounds of the general formula (VIII), the sum of p
and q is preferably a value of 10 to 300, more preferably of 15 to
200 and especially of 20 to 150.
[0299] In the compounds of the general formula (VIII), R.sup.16 and
R.sup.18 are preferably each independently a straight-chain or
branched saturated C.sub.4-C.sub.30-alkyl radical. At the same
time, R.sup.16 and R.sup.18 may also be mixtures of different alkyl
radicals.
[0300] In the compounds of the general formula (VIII), R.sup.17 is
preferably methyl or ethyl, especially methyl.
[0301] These include, for example, lauryl alcohol polyoxyethylene
acetate. [0302] alkylaryl alcohol polyoxyethylene ethers, e.g.
octylphenol polyoxyethylene ethers, [0303] alkoxylated animal
and/or vegetable fats and/or oils, for example corn oil
ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, [0304]
alkylphenol alkoxylates, for example ethoxylated isooctyl-, octyl-
or nonylphenol, tributylphenol polyoxyethylene ether, [0305] fatty
amine alkoxylates, fatty acid amide and fatty acid diethanolamide
alkoxylates, especially ethoxylates thereof, [0306] polyoxyalkylene
sorbitan fatty acid esters.
[0307] One example of an alkyl polyether sulfate is sodium dodecyl
poly(oxyethylene) sulfate (sodium lauryl ether sulfate, SLES). A
preferred commercially available modified fatty alcohol polyglycol
ether is a polyethylene oxide
C.sub.xH.sub.2x+1/C.sub.yH.sub.2y+1-terminated at either end and
having a free OH group and x, y=6-14.
[0308] Polymer P2)
[0309] The multilayer film of the invention comprises at least one
layer comprising or consisting of a polymer composition P1).
Preferably, the multilayer film of the invention comprises at least
one further layer comprising or consisting of at least one polymer
P2) other than the polymers present in the polymer composition
P1).
[0310] In a preferred embodiment, the individual layers of the
multilayer films of the invention are water-soluble or
water-dispersible. According to the field of use of the multilayer
films of the invention, it may be advantageous for the individual
layers to have a particular solubility in water. For example, it
may be desirable for different layers to have different solubility
in water. It may also be desirable, for example, for an outer
surface layer to have a lesser degree of water solubility in order
to prevent blocking and/or partial dissolution in the event of high
air humidity and/or high contact moisture (e.g. hand moisture).
Alternatively, it may also be desirable for an outer surface layer
to have high water solubility in order to rapidly release an active
ingredient present therein or ensheathed therewith on contact with
water. Such a film may then have water-insoluble outer packaging to
prevent unwanted contact with water.
[0311] According to the field of use of the multilayer films of the
invention, it may also be advantageous for the individual layers to
have a temperature-dependent solubility in water.
[0312] The multilayer film of the invention preferably comprises at
least one further layer comprising or consisting of at least one
polymer P2) selected from [0313] natural and modified
polysaccharides, [0314] homo- and copolymers comprising repeat
units which derive from vinyl alcohol, vinyl esters, alkoxylated
vinyl alcohols or mixtures thereof, [0315] homo- and copolymers
comprising at least one copolymerized monomer selected from
N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole,
2-vinylpyridine, 4-vinylpyridine, salts of the three latter
monomers, vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridium
halides and mixtures thereof, [0316] homo- and copolymers of
acrylic acid and/or methacrylic acid, especially copolymers
comprising at least one copolymerized acrylic monomer selected from
acrylic acid, acrylic salts and mixtures thereof, and at least one
copolymerized maleic monomer selected from maleic acid, maleic
anhydride, maleic salts and mixtures thereof, [0317] copolymers
comprising at least one copolymerized (meth)acrylic monomer
selected from acrylic acid, methacrylic acid, salts thereof and
mixtures thereof and at least one copoylmerized hydrophobic monomer
selected from C.sub.1-C.sub.8-alkyl esters of (meth)acrylic acid,
C.sub.2-C.sub.10 olefins, styrene and .alpha.-methylstyrene,
copolymers comprising at least one copolymerized maleic monomer
selected from maleic acid, maleic anhydride, maleic salts and
mixtures thereof and at least one copolymerized C.sub.2-C.sub.8
olefin, [0318] homo- and copolymers of acrylamide and/or
methacrylamide, [0319] polyamino acids, [0320] water-soluble or
water-dispersible polyamides, [0321] polyalkylene glycols, mono- or
diethers of polyalkylene glycols, and [0322] mixtures thereof.
[0323] The multilayer film of the invention more preferably
comprises at least one further layer comprising or consisting of at
least one polymer P2) selected from [0324] cellulose ethers and
cellulose esters, [0325] homo- and copolymers comprising repeat
units which derive from vinyl alcohol, vinyl esters, alkoxylated
vinyl alcohols or mixtures thereof, [0326] polymers selected from
polyvinylpyrrolidone homopolymers, polyvinylimidazole homopolymers,
copolymers comprising copolymerized vinylpyrrolidone and
vinylimidazole, polyvinylpyridine N-oxide,
poly-N-carboxymethyl-4-vinylpyridium halides, [0327] mixtures
thereof.
[0328] The multilayer film of the invention especially comprises at
least one further layer comprising or consisting of at least one
polymer P2) selected from cellulose derivatives, preferably
carboxyalkyl celluloses and salts thereof, sulfoalkyl celluloses
and salts thereof, acidic sulfuric ester salts of cellulose, alkyl
celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses
and mixtures of two or more of these cellulose derivatives.
[0329] Polysaccharides suitable as polymers P2) are natural
polysaccharides, for example cellulose, hemicellulose, xyloglucan,
glycogen, starch (amylose and amylopectin), dextran, pectins,
inulin, xanthan, chitin, callose, and thermally, hydrolytically or
enzymatically degraded starch, e.g. maltodextrin etc.
[0330] Preferred modified polysaccharides are, for example,
cellulose ethers, cellulose esters, cellulose amides, etc.
[0331] Cellulose ethers are derivatives of cellulose which arise
through partial or complete substitution of the hydrogen atoms in
the hydroxyl groups of the cellulose. Cellulose ethers from the
reaction of cellulose with more than one etherifying agent are also
referred to as cellulose mixed ethers.
[0332] Preferred cellulose ethers are selected from alkyl
celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses,
carboxyalkyl celluloses and salts thereof, carboxyalkyl alkyl
celluloses and salts thereof, carboxyalkyl hydroxyalkyl celluloses
and salts thereof, carboxyalkyl hydroxyalkyl alkyl celluloses and
salts, sulfoalkyl celluloses and salts thereof.
[0333] Preferred carboxyalkyl radicals are the carboxymethyl
radical and the carboxyethyl radical. A particularly preferred
carboxyalkyl radical is the carboxymethyl radical. Preferred
sulfoalkyl radicals are the sulfomethyl radical and the sulfoethyl
radical. A particularly preferred sulfoalkyl radical is the
sulfomethyl radical. Preferred salts are the sodium, potassium,
calcium and ammonium salts.
[0334] Particularly preferred cellulose ethers are selected from
carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose,
ethyl cellulose, n-propyl cellulose, ethyl methyl cellulose,
hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl
cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl
cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl ethyl
cellulose, carboxymethyl methyl cellulose, carboxymethyl ethyl
cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl
hydroxyethyl methyl cellulose, carboxymethyl hydroxyethyl ethyl
cellulose, sulfomethyl cellulose and sulfoethyl cellulose. The
carboxyalkyl radicals and the sulfoalkyl radicals may also be in
salt form.
[0335] Cellulose esters are derivatives of cellulose which form as
a result of esterification of the hydroxyl groups with acids.
Preference is given to the sulfuric esters of cellulose. In a
specific embodiment, the sulfuric acid is subjected only to a
partial esterification, such that the resulting sulfuric esters
still have free acid groups or salts thereof. Particular preference
is given to using acidic sulfuric ester salts of cellulose. These
are notable for their graying-inhibiting effect.
[0336] Preferred modified polysaccharides are selected from methyl
cellulose, ethyl cellulose, propyl cellulose, methyl/ethyl
cellulose, ethyl/propyl cellulose, carboxymethyl cellulose, salts
of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl
cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl
cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl
cellulose, etc.
[0337] In a further preferred embodiment, the polymers P2) are
selected from homo- and copolymers comprising repeat units which
derive from vinyl alcohol, vinyl esters, alkoxylated vinyl alcohols
or mixtures thereof.
[0338] Suitable vinyl esters (vinyl acylates) are generally the
esters of vinyl alcohol with C.sub.1-C.sub.15 carboxylic acids,
preferably C.sub.1-C.sub.8 carboxylic acids, more preferably
C.sub.1-C.sub.4 carboxylic acids. Preferred vinyl acylates are
vinyl acetate, vinyl n-propionate, vinyl n-butyrate, vinyl
2-ethylhexanoate, vinyl laurate, etc. Particular preference is
given to vinyl acetate.
[0339] Partly or fully hydrolyzed polyvinyl acetates (PVAs) are
generally referred to as "polyvinyl alcohol (PVOH)". Partly
hydrolyzed polyvinyl acetates are obtained by incomplete hydrolysis
of polyvinyl acetates, meaning that the partly hydrolyzed polymer
has both ester groups and hydroxyl groups. The hydrolysis of the
polyvinyl acetates can be effected in a manner known per se under
alkaline or acidic conditions, i.e. with addition of acid or
base.
[0340] The performance properties of polyvinyl alcohols are
determined by factors including the polymerization level and the
hydrolysis level (level of hydrolysis). With rising hydrolysis
level, the water solubility decreases. Polyvinyl alcohols having
hydrolysis levels up to about 90 mol % are generally soluble in
cold water. Polyvinyl alcohols having hydrolysis levels of about 90
to about 99.9 mol % are generally no longer soluble in cold water
but are soluble in hot water.
[0341] Polyvinyl alcohols suitable as polymers P2) preferably have
a hydrolysis level of 50 to 99.9 mol %, more preferably of 70 to 99
mol %, especially of 80 to 98 mol %.
[0342] Polyvinyl alcohols suitable as polymers P2) preferably have
a weight-average molecular weight of 10 000 to 300 000 g/mol, more
preferably of 15 000 to 250 000 g/mol.
[0343] Polyvinyl alcohols suitable as polymers P2) preferably have
a viscosity of 2 to 120 mPas, more preferably of 7 to 70 mPas and
especially of 15 to 60 mPas, measured to DIN 53015 on a 4% solution
in water.
[0344] In a further preferred embodiment, the polymers P2) are
selected from homo- and copolymers comprising at least one
copolymerized monomer selected from N-vinylpyrrolidone,
N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine,
4-vinylpyridine, salts of the three latter monomers, vinylpyridine
N-oxide, N-carboxymethyl-4-vinylpyridium halides and mixtures
thereof.
[0345] N-Vinylimidazole, 2-vinylpyridine and 4-vinylpyridine can be
converted to the corresponding salts by protonation or
quaternization. Suitable acids are, for example, mineral acids such
as sulfuric acid, hydrochloric acid and phosphoric acid, and
carboxylic acids. Alkylating agents suitable for quaternization are
C.sub.1-C.sub.4-alkyl halides or C.sub.1-C.sub.4-alkyl sulfates,
such as ethyl chloride, ethyl bromide, methyl chloride, methyl
bromide, dimethyl sulfate and diethyl sulfate.
[0346] Preference is given to polyvinylpyrrolidone homopolymers and
copolymers comprising copolymerized N-vinylpyrrolidone and another
different copolymerized ethylenically unsaturated monomer. Suitable
N-vinylpyrrolidone copolymers are quite generally uncharged,
anionic, cationic and amphoteric polymers.
[0347] Particularly preferred N-vinylpyrrolidone copolymers are
selected from
[0348] copolymers of N-vinylpyrrolidone and vinyl acetate,
[0349] copolymers of N-vinylpyrrolidone and vinyl propionate,
[0350] copolymers of N-vinylpyrrolidone, vinyl acetate and vinyl
propionate,
[0351] copolymers of N-vinylpyrrolidone and vinyl acrylate,
[0352] copolymers of N-vinylpyrrolidone, ethyl methacrylate and
methacrylic acid,
[0353] copolymers of N-vinylpyrrolidone and N-vinylimidazole and
the derivatives thereof obtained by protonation and/or
quaternization,
[0354] copolymers of N-vinylpyrrolidone and dimethylaminoethyl
methacrylate and the derivatives thereof obtained by protonation
and/or quaternization,
[0355] copolymers of N-vinylpyrrolidone, N-vinylcaprolactam and
N-vinylimidazole and the derivatives thereof obtained by
protonation and/or quaternization.
[0356] In a further preferred embodiment, the polymers P2) are
selected from homo- and copolymers of acrylic acid and/or
methacrylic acid.
[0357] In a first specific embodiment of the homo- and copolymers
of acrylic acid and/or methacrylic acid, the polymer P2) used is an
acrylic acid homopolymer. Acrylic acid homopolymers P2) preferably
have a number-average molecular weight in the range from 800 to 70
000 g/mol, more preferably 900 to 50 000 g/mol, particularly 1000
to 20 000 g/mol and especially 1000 to 10 000 g/mol. In this
context, the term "acrylic acid homopolymer" also encompasses
polymers in which the carboxylic acid groups are in partly or fully
neutralized form. These include acrylic acid homopolymers in which
the carboxylic acid groups are present partly or completely in the
form of alkali metal salts or ammonium salts. Preference is given
to acrylic acid homopolymers in which the carboxylic acid groups
are protonated or are partly or completely in the form of sodium
salts. Homopolymers of acrylic acid particularly suitable as
polymers P2) are the Sokalan.RTM. PA brands from BASF SE.
[0358] In a second specific embodiment of the homo- and copolymers
of acrylic acid and/or methacrylic acid, polymer P2) used is a
copolymer comprising at least one copolymerized acrylic acid
monomer selected from acrylic acid, acrylic salts and mixtures
thereof and at least one copolymerized maleic monomer selected from
maleic acid, maleic anhydride, maleic salts and mixtures thereof.
These preferably have a number-average molecular weight in the
range from 2500 to 150 000 g/mol, more preferably 2800 to 70 000
g/mol, particularly 2900 to 50 000 g/mol and especially 3000 to 30
000 g/mol. Also included here are copolymers in which the
carboxylic acid groups are in partly or fully neutralized form. For
this purpose, it is either possible to use monomers in salt form
for polymerization or for the resulting copolymer to be subjected
to partial or complete neutralization. Preference is given to
copolymers in which the carboxylic acid groups are protonated or
are partly or completely in the form of alkali metal salts or
ammonium salts. Preferred alkali metal salts are sodium or
potassium salts, especially the sodium salts.
[0359] Preferred polymers P2) are copolymers of maleic acid (or
maleic monomers) and acrylic acid (or acrylic monomers) in a weight
ratio of 10:90 to 95:5, more preferably those in a weight ratio of
30:70 to 90:10.
[0360] Preferred polymers P2) are also terpolymers of maleic acid
(or maleic monomers), acrylic acid (or acrylic monomers) and a
vinyl ester of a C.sub.1-C.sub.3 carboxylic acid in a weight ratio
of 10 (maleic acid):90 (acrylic acid+vinyl ester) to 95 (maleic
acid):10 (acrylic acid+vinyl ester). The weight ratio of acrylic
acid to vinyl ester is preferably within a range from 30:70 to
70:30.
[0361] Particularly suitable polymers P2) based on acrylic monomers
and maleic monomers are the corresponding Sokalan.RTM. CP brands
from BASF SE.
[0362] In a third specific embodiment of the homo- and copolymers
of acrylic acid and/or methacrylic acid, polymer P2) used is a
copolymer comprising at least one (meth)acrylic acid monomer
selected from (meth)acrylic acid, (meth)acrylic salts and mixtures
thereof and at least one hydrophobic monomer. The hydrophobic
monomer is especially selected from C.sub.1-C.sub.8-alkyl esters of
(meth)acrylic acid, for example the methyl, ethyl, n- and
isopropyl, n-butyl and 2-ethylhexyl esters of (meth)acrylic acid
and C.sub.2-C.sub.10 olefins, for example ethene, propene,
1,2-butene, isobutene, diisobutene, styrene and
.alpha.-methylstyrene.
[0363] In a further preferred embodiment, the polymer P2) used is a
copolymer of at least one maleic monomer selected from maleic acid,
maleic anhydride, maleic salts and mixtures thereof with at least
one C.sub.2-C.sub.8 olefin. Also suitable are copolymers comprising
at least one copolymerized maleic monomer selected from maleic
acid, maleic anhydride, maleic salts and mixtures thereof, at least
one copolymerized C.sub.2-C.sub.8 olefin and at least one other
different copolymerized comonomer.
[0364] Particular preference is given to copolymers comprising at
least one copolymerized maleic monomer selected from maleic acid,
maleic anhydride, maleic salts and mixtures thereof and at least
one copolymerized C.sub.2-C.sub.8 olefin as the sole monomers.
These preferably have a number-average molecular weight in the
range from 3000 to 150 000 g/mol, more preferably 5000 to 70 000
g/mol, particularly 8000 to 50 000 g/mol and especially 10 000 to
30 000 g/mol. Also included here are copolymers in which the
carboxylic acid groups are in partly or fully neutralized form. For
this purpose, it is either possible to use maleic salts for
polymerization or for the resulting copolymer to be subjected to
partial or complete neutralization. Preference is given to
copolymers in which the carboxylic acid groups are protonated or
are partly or completely in the form of alkali metal salts or
ammonium salts. Preferred alkali metal salts are sodium or
potassium salts, especially the sodium salts.
[0365] A specific embodiment is copolymers of maleic acid with
C.sub.2-C.sub.8 olefins in a molar ratio of 40:60 to 80:20,
particular preference being given to copolymers of maleic acid with
ethylene, propylene, isobutene, diisobutene or styrene.
Particularly suitable compounds which contain carboxylic acid
groups and are based on olefins and maleic acid are likewise the
corresponding Sokalan.RTM. CP brands from BASF SE.
[0366] A further preferred embodiment is that of copolymers
comprising at least one copolymerized maleic monomer selected from
maleic acid, maleic anhydride, maleic salts and mixtures thereof,
at least one copolymerized C.sub.2-C.sub.8 olefin and at least one
copolymerized acrylic monomer selected from acrylic acid, acrylic
salts and mixtures thereof.
[0367] A further preferred embodiment is that of copolymers
comprising at least one copolymerized maleic monomer selected from
maleic acid, maleic anhydride, maleic salts and mixtures thereof,
at least one copolymerized C.sub.2-C.sub.8 olefin and at least one
copolymerized ester of (meth)acrylic acid. In that case, the ester
of (meth)acrylic acid is especially selected from
C.sub.1-C.sub.8-alkyl esters of (meth)acrylic acid, for example the
methyl, ethyl, n- and isopropyl, n-butyl and 2-ethylhexyl esters of
(meth)acrylic acid.
[0368] In a further preferred embodiment, the polymers P2) are
selected from homo- and copolymers comprising at least one
copolymerized monomer selected from acrylamide, methacrylamide and
mixtures thereof. These polymers P2) are preferably water-soluble
or water-dispersible. These polymers P2) are especially
water-soluble.
[0369] In a specific embodiment, the polymers P2) are selected from
homopolymers of acrylamide or methacrylamide.
[0370] In a further specific embodiment, the polymers P2) are
selected from copolymers of acrylamide and/or methacrylamide. These
comprise at least one copolymerized comonomer selected from
hydrophilic monomers (A1) other than acrylamide and methacrylamide,
monoethylenically unsaturated amphiphilic monomers (A2) and further
ethylenically unsaturated monomers (A3).
[0371] Suitable hydrophilic monoethylenically unsaturated monomers
(A1) are uncharged monomers such as N-methyl(meth)acrylamide,
N,N'-dimethyl(meth)acrylamide or N-methylol(meth)acrylamide,
monomers comprising hydroxyl and/or ether groups, for example
hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl
alcohol, hydroxyvinyl ethyl ether, hydroxyvinyl propyl ether,
hydroxyvinyl butyl ether, polyethylene glycol (meth)acrylate,
N-vinylformamide, N-vinylacetamide, N-vinyl-pyrrolidone or
N-vinylcaprolactam, and vinyl esters, for example vinyl formate or
vinyl acetate. After polymerization, N-vinyl derivatives may be
hydrolyzed to vinylamine units, and vinyl esters to vinyl alcohol
units. Suitable hydrophilic monoethylenically unsaturated monomers
(A1) are also monomers comprising at least one acidic group or
salts thereof. These include acrylic acid, methacrylic acid,
crotonic acid, itaconic acid, maleic acid, fumaric acid,
vinylsulfonic acid, allylsulfonic acid,
2-acrylamido-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylpropanesulfonic acid,
2-acryl-amidobutanesulfonic acid,
3-acrylamido-3-methylbutanesulfonic acid,
2-acrylamido-2,4,4-trimethylpentanesulfonic acid, vinylphosphonic
acid, allylphosphonic acid, N-(meth)acrylamidoalkylphosphonic
acids, (meth)acryloyloxyalkylphosphonic acids and salts and
mixtures thereof. The further monoethylenically unsaturated
hydrophilic monomers may be hydrophilic cationic monomers. Suitable
cationic monomers (A1c) especially include monomers having ammonium
groups, especially ammonium derivatives of
N-(w-aminoalkyl)(meth)acrylamides or w-aminoalkyl
(meth)acrylates.
[0372] The amphiphilic monomers (A2) are monoethylenically
unsaturated monomers having at least one hydrophilic group and at
least one, preferably terminal, hydrophobic group.
[0373] The monomers (A3) may, for example, be monoethylenically
unsaturated monomers which have a more hydrophobic character than
the hydrophilic monomers (A1) and are accordingly water-soluble
only to a minor degree. Examples of such monomers include N-alkyl-
and N,N'-dialkyl(meth)acrylamides, where the number of carbon atoms
in the alkyl radicals together is at least 3, preferably at least
4. Examples of such monomers include N-butyl(meth)acrylamide,
N-cyclohexyl(meth)acrylamide or N-benzyl(meth)acrylamide.
[0374] In a further preferred embodiment, the polymers P2) are
selected from polyamino acids. Suitable polyamino acids are in
principle compounds comprising at least one copolymerized amino
acid such as aspartic acid, glutamic acid, lysine, glycine, etc.
The polyamino acids also include the derivatives obtainable by
polymer-analogous reaction, such as esterification, amidation, etc.
Preferred polyamino acids are polyaspartic acid, polyaspartic acid
derivatives, polyglutamic acid, polyglutamic acid derivatives and
mixtures thereof.
[0375] Polyaspartic acid can be prepared, for example, by alkaline
hydrolysis of polysuccinimide (PSI, anhydropolyaspartic acid).
Polysuccinimide can be prepared by thermal condensation of aspartic
acid or from ammonia and maleic acid. Polyaspartic acid can be
used, for example, as a biodegradable complexing agent and
cobuilder in washing and cleaning compositions.
[0376] Polyamino acids having surfactant properties can be obtained
by at least partly converting the free carboxylic acid groups of
polyaspartic acid or polyglutamic acid to N-alkylamides and/or to
esters. Polyaspartamides can also be prepared by reaction of
polysuccinimide with amines. For preparation of
hydroxylethylaspartamides, the ring opening of polysuccinimide can
be conducted with ethanolamine. DE 37 00 128 A and EP 0 458 079 A
describe the subsequent esterification of such hydroxyethyl
derivatives with carboxylic acid derivatives. Copolymeric
polyaspartic esters are obtainable as described in DE 195 45 678 A
by condensation of monoalkyl esters of maleic or fumaric acid with
addition of ammonia. DE 195 45 678 A further states that
copolymeric polyaspartic esters are obtainable by reaction of
polysuccinimide with alcohols, optionally followed by hydrolysis.
According to the esterification level and hydrophobicity of the
alcohol component, polyaspartic esters, aside from their
biodegradability, are notable for excellent properties as
stabilizers for O/W and W/O emulsions, as a foam-stabilizing and
foam-boosting cosurfactant in washing and cleaning compositions,
and as a complexing agent for metal cations.
[0377] In a further preferred embodiment, the polymers P2) are
selected from polyalkylene glycols and mono- or diethers of
polyalkylene glycols. Preferred polyalkylene glycols have a
number--average molecular weight in the range from 1000 to 4 000
000 g/mol, more preferably from 1500 to 1 000 000 g/mol.
[0378] Suitable polyalkylene glycols and the mono- and diethers
thereof may be linear or branched, preferably linear. Suitable
polyalkylene glycols are, for example, water-soluble or
water-dispersible nonionic polymers having repeat alkylene oxide
units. Preferably, the proportion of repeat alkylene oxide units is
at least 30% by weight, preferably at least 50% by weight and
especially at least 75% by weight, based on the total weight of the
compound. Suitable polyalkylene glycols are polyethylene glycols,
polypropylene glycols, polytetrahydrofurans and alkylene oxide
copolymers. Suitable alkylene oxides for preparation of alkylene
oxide copolymers are, for example, ethylene oxide, propylene oxide,
epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable examples are
copolymers of ethylene oxide and propylene oxide, copolymers of
ethylene oxide and butylene oxide, and copolymers of ethylene
oxide, propylene oxide and at least one butylene oxide. The
alkylene oxide copolymers may comprise the copolymerized alkylene
oxide units in randomly distributed form or in the form of blocks.
Preferably, the proportion of repeat units derived from ethylene
oxide in the ethylene oxide/propylene oxide copolymers is 40% to
99% by weight. Particular preference is given to ethylene oxide
homopolymers and ethylene oxide/propylene oxide copolymers.
[0379] Suitable mono- and diethers of polyalkylene glycols are the
mono-(C.sub.1-C.sub.18-alkyl) ethers and
di-(C.sub.1-C.sub.18-alkyl) ethers. Preferred mono- and diethers of
polyalkylene glycols are the mono-(C.sub.1-C.sub.6-alkyl) ethers
and di-(C.sub.1-C.sub.6-alkyl) ethers. Especially preferred are the
mono-(C.sub.1-C.sub.2-alkyl) ethers and di-(C.sub.1-C.sub.2-alkyl)
ethers. Especially preferred are polyalkylene glycol monomethyl
ethers and polyalkylene glycol dimethyl ethers.
[0380] Polymer mixtures are suitable, for example, for adjusting
the mechanical properties and/or the dissolution properties of the
multilayer films of the invention. The polymers used in the polymer
mixture may differ in terms of their chemical composition and/or in
terms of their physicochemical properties.
[0381] In a specific embodiment, the multilayer film of the
invention comprises at least one layer comprising a mixture of 2 or
more polymers. Suitable mixtures may comprise 2 or more different
polymer compositions P1) or at least one polymer composition P1)
and at least one polymer P2) or 2 or more different polymers
P2).
[0382] In a first embodiment, a polymer mixture comprising 2 or
more polymers which differ in terms of their chemical composition
is used. In a second embodiment, a polymer mixture comprising 2 or
more polymers which differ in terms of their molecular weight is
used. According to this second embodiment, for example, a polymer
mixture comprising at least two polymers P2) comprising repeat
units which derive from vinyl alcohol is used.
[0383] Characterization of the Multilayer Film
[0384] The multilayer film of the invention consists preferably of
2 to 20 layers, more preferably 2 to 15 layers and especially 2 to
10 layers. These specifically include multilayer films consisting
of 2, 3, 4, 5, 6, 7 or 8 layers. All these layers may be of
different composition, or two or more than two of the layers may
have the same composition. The composition of the individual layers
depends on the field of use of the multilayer film of the
invention.
[0385] Preferably, the multilayer films of the invention have a
total polymer weight (i.e. of all the components P1) and P2)
present) per layer in the range from 0.1 to 100 mg/cm.sup.2 of
film, more preferably of 1 to 80 mg/cm.sup.2 of film.
[0386] As explained above, the layer thickness of the multilayer
films of the invention is variable within wide ranges and is
dependent on the field of use of the multilayer films of the
invention.
[0387] Preferably, the multilayer films of the invention for
ensheathing or coating a washing, cleaning or dishwashing
composition have a layer thickness per layer in the range from 0.5
to 500 .mu.m, preferably from 1 to 250 .mu.m.
[0388] Preferably, two-layer films of the invention for ensheathing
or coating a washing, cleaning or dishwashing composition have a
total layer thickness in the range from 1 to 1000 .mu.m, preferably
from 2 to 750 .mu.m.
[0389] Preferably, three-layer films of the invention for
ensheathing or coating a washing, cleaning or dishwashing
composition have a total layer thickness in the range from 1.5 to
1500 .mu.m, preferably from 2 to 1250 .mu.m.
[0390] As explained above, multilayer films which themselves serve
as washing compositions or as cleaning compositions or as
dishwashing compositions preferably have a thickness of not more
than 30 mm, more preferably not more than 25 mm.
[0391] The multilayer films of the invention feature good
mechanical properties. These are shown, for example, in tensile
tests on film strips of the multilayer films as described in
standards EN ISO 527-1 and ASTM D882-12. EN ISO 527-1 (current ISO
version February 2012) is a European standard for plastics for
determination of the tensile properties, which are ascertained by a
tensile test with a tensile tester. For these tests, it is possible
to use a standard apparatus, for example a universal tester from
Zwick GmbH, model TMTC-FR2.5TN.D09. To achieve homogeneous test
conditions, the multilayer films can first be subjected to storage
for several days in equilibrium with the ambient humidity (35-40%
relative humidity at 20-25.degree. C.).
[0392] Tensile strength is a material property which states the
maximum mechanical tensile stress that the material withstands
before breaking/tearing. Preferably, the multilayer films of the
invention have a tensile strength in the range from 3 to 40
N/mm.sup.2.
[0393] Elongation is a dimensionless parameter which is reported in
percent. Preferably, the multilayer films of the invention have an
elongation of 20% to 500%.
[0394] Production of the Multilayer Films
[0395] The multilayer films of the invention comprise at least one
layer comprising or consisting of a polymer composition P1).
[0396] Preferably, the polymer composition P1) is produced by
[0397] A) providing a monomer composition M1) comprising at least
one monomer A) selected from .alpha.,.beta.-ethylenically
unsaturated mono- and dicarboxylic acids, salts of
.alpha.,.beta.-ethylenically unsaturated mono- and dicarboxylic
acids, anhydrides of .alpha.,.beta.-ethylenically unsaturated mono-
and dicarboxylic acids and mixtures thereof, [0398] B) subjecting
the monomer composition M1) provided in step A) to a free-radical
polymerization in the presence of at least one polyether component
PE) selected from polyetherols having a number-average molecular
weight of at least 200 g/mol, mono- and di(C.sub.1-C.sub.6-alkyl)
ethers thereof, surfactants containing polyether groups and
mixtures thereof, optionally in the presence of at least one
additive.
[0399] With regard to the monomer composition provided in step A),
reference is made in full to the aforementioned suitable and
preferred monomers A) and the optional comonomers B) and C).
[0400] The free-radical polymerization of the monomer composition
M1) in step B) is preferably conducted by the feed method. This
generally involves metering at least the monomers in liquid form
into the reaction mixture. Monomers which are liquid under the
metering conditions can be fed into the reaction mixture without
addition of a solvent S1); otherwise, the monomers are used as a
solution in a suitable solvent S1). It is of course also possible
to use monomers that are in solid form.
[0401] The free-radical polymerization for production of the
polymer composition P1) can be effected in the presence of a
solvent S1) selected from water, C.sub.1-C.sub.6-alkanols, polyols
other than PE) and the mono- and dialkyl ethers and mixtures
thereof. Suitable polyols and the mono- and dialkyl ethers thereof
also include alkylene glycol mono(C.sub.1-C.sub.4-alkyl) ethers,
alkylene glycol diC.sub.1-C.sub.4-alkyl) ethers, oligoalkylene
glycols and mono(C.sub.1-C.sub.4-alkyl) ethers and
diC.sub.1-C.sub.4-alkyl) ethers thereof.
[0402] The solvent S1) is preferably selected from water, methanol,
ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol,
ethylene glycol mono(C.sub.1-C.sub.4-alkyl) ethers, ethylene glycol
diC.sub.1-C.sub.4-alkyl) ethers, 1,2-propylene glycol,
1,2-propylene glycol mono(C.sub.1-C.sub.4-alkyl) ethers,
1,2-propylene glycol diC.sub.1-C.sub.4-alkyl) ethers, glycerol,
polyglycerols, oligoalkylene glycols having a number-average
molecular weight of less than 1000 g/mol and mixtures thereof.
[0403] Suitable oligoethylene glycols are commercially available
under the CTFA names PEG-6, PEG-8, PEG-12, PEG-6-32, PEG-20,
PEG-150, PEG-200, PEG-400, PEG-7M, PEG-12M and PEG-115M. These
specifically include the Pluriol E.RTM. brands from BASF SE.
Suitable alkyl polyalkylene glycols are the corresponding Pluriol A
. . . E.RTM. brands from BASF SE.
[0404] The solvent S1) is more preferably selected from water,
ethanol, n-propanol, isopropanol, ethylene glycol, diethylene
glycol, triethylene glycol, 1,2-propylene glycol, 1,2-dipropylene
glycol and mixtures thereof.
[0405] In a specific embodiment, the solvent S1) used is selected
from water and a mixture of water and at least one solvent S1)
other than water, selected from ethanol, n-propanol, isopropanol,
ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,2-dipropylene glycol and mixtures
thereof.
[0406] In a specific embodiment, the free-radical polymerization in
step B) is effected in the presence of a solvent S1) consisting to
an extent of at least 50% by weight, preferably to an extent of at
least 75% by weight and especially to an extent of at least 90% by
weight, based on the total weight of the solvent S1), of water.
More particularly, the free-radical polymerization in step B) is
effected in the presence of a solvent S1) consisting entirely of
water.
[0407] Preferably, the free-radical polymerization in step B) is
effected in feed mode, in which case feeds comprising at least one
.alpha.,.beta.-ethylenically unsaturated carboxylic acid do not
comprise any solvent S1).
[0408] The metering rates of the monomer feed(s) and any further
feeds (initiator, chain transfer agent, etc.) are preferably
selected such that the polymerization is maintained with the
desired conversion rate. The addition of the individual feeds here
may be continuous, periodical, with constant or changing metering
rate, essentially simultaneous or at different times. Preferably,
the addition of all the feeds to the reaction mixture is
continuous.
[0409] Preferably, for the free-radical polymerization, the monomer
composition M1) and the polyether component PE) are used in a
weight ratio of 0.5:1 to 5:1, more preferably of 0.7:1 to 3:1.
[0410] If the polymer composition P1) is produced using a solvent
S1), the weight ratio of the polyether component PE) to the
component S1) is preferably in the range from 0.1:1 to 5:1, more
preferably from 0.5:1 to 3:1.
[0411] Preferably, the free-radical polymerization in step B) is
effected at a temperature in the range from 20 to 95.degree. C.,
more preferably from 30 to 90.degree. C., especially from 40 to
80.degree. C.
[0412] The free-radical polymerization in step B) can be effected
in the presence of at least one additive. Suitable additives are,
for example, corrosion inhibitors, defoamers and foam inhibitors,
dyes, fragrances, bitter substances, thickeners, solubilizers,
organic solvents, electrolytes, antimicrobial active ingredients,
antioxidants, UV absorbers and mixtures thereof.
[0413] Preferably, the free-radical polymerization in step B) of
the process comprises [0414] B1) providing an initial charge
comprising at least a portion of the polyether component PE),
optionally at least a portion of the chain transfer agent CTA) and,
if the polymerization is effected in the presence of a solvent S1),
optionally at least a portion of S1); [0415] B2) adding the monomer
composition M1) in one or more feed(s) and adding a feed comprising
the free-radical initiator FRI), dissolved in a portion of at least
one polyether component PE) and/or of the solvent S1), and
optionally adding a feed comprising the amount of the chain
transfer agent CTA) which is not used in the initial charge; [0416]
B3) optional post-polymerization of the reaction mixture obtained
in step B2).
[0417] Typically, the initial charge is heated to the
polymerization temperature before the feeds are added while
stirring.
[0418] Preferably, the individual reactants are added
simultaneously in separate feeds, the flow rates of the feeds
generally being kept very substantially constant over the period of
addition.
[0419] Preferably, the amount of polyether component PE) in the
initial charge (step B1)) is 30% to 100% by weight, more preferably
65% to 100% by weight and especially 80% to 100% by weight, based
on the total weight of the polyether component PE) used for
polymerization.
[0420] Preferably, the content of solvent S1) in the initial charge
is not more than 70% by weight, based on the total weight of the
feedstocks in the initial charge. Preferably, the content of
solvent in the initial charge is not more than 40% by weight,
especially not more than 35% by weight, based on the total weight
of the feedstocks in the initial charge. The amount of solvent
generally changes only by a few percent by weight over the entire
course of the process. Typically, solvents S1) having a boiling
point at standard pressure (1 bar) of below 240.degree. C. are
used.
[0421] In a specific variant, the initial charge does not comprise
any solvent. The solvent is not added until step B2), via at least
one of the feeds. In a very specific variant, no solvent is
included in the initial charge and no solvent is added over the
entire course of the process.
[0422] In a further specific variant, the solvent is initially
charged in its entirety.
[0423] In a further specific variant, the initial charge does not
comprise any chain transfer agent. If a chain transfer agent is
used, this is not added until step B2), via at least one of the
feeds.
[0424] The feeds are added in step B2) over a period of time which
is advantageously selected such that the heat of reaction that
arises in the course of the exothermic polymerization reaction can
be removed without any great technical complexity, for example
without the use of a reflux condenser. Typically, the feeds are
added over a period of 1 to 10 hours. Preferably, the feeds are
added over a period of 2 to 8 hours, more preferably over 2 to 6
hours.
[0425] In an alternative embodiment, the free-radical
polymerization in step B) of the process is continuous. In that
case, the monomer composition M1), the polyether component PE), at
least one initiator, optionally at least one chain transfer agent
CTA) and optionally at least one solvent S1) are added to the
reactor in the form of one liquid stream or preferably at least two
liquid streams. In general, the stream comprising the initiator
generally does not comprise the chain transfer agent as well. If at
least two liquid streams are used, these are typically mixed to
obtain the reaction mixture. The polymerization can be effected in
one stage or in two or more than two, i.e. in 2, 3, 4, 5 or more,
stages. In a suitable embodiment, in the case of a multistage
polymerization, at least one additional stream is mixed in between
at least two of the polymerization stages. This may be a
monomer-containing stream, initiator-containing stream,
solvent-containing stream, chain transfer agent-containing stream,
a mixture thereof and/or any other stream of matter.
[0426] During the free-radical polymerization, the optionally used
solvent and/or any condensation products that form are generally
not removed. In other words, during the polymerization, there is
typically only very minor mass transfer with the surroundings, if
any, within the scope of the technical options.
[0427] The polymerization can generally be effected at ambient
pressure or reduced or elevated pressure. Preferably, the
polymerization is conducted at ambient pressure.
[0428] The polymerization is generally effected at constant
temperature, but it can also be varied during the polymerization if
required. Preferably, the polymerization temperature is kept very
substantially constant over the entire reaction period, i.e. steps
B2) and B3). According to the feedstocks which are used in the
process of the invention, the polymerization temperature varies
typically within the range from 20 to 95.degree. C. Preferably, the
polymerization temperature varies within the range from 30 to
90.degree. C. and especially within the range from 40 to 80.degree.
C. If the polymerization is not conducted under elevated pressure
and at least one optional solvent S1) has been added to the
reaction mixture, the solvent or solvent mixture determines the
maximum reaction temperature by virtue of the corresponding boiling
temperatures.
[0429] The polymerization can be effected in the absence or
presence of an inert gas. Typically, the polymerization is
conducted in the presence of an inert gas. Inert gas is generally
understood to mean a gas which, under the given reaction
conditions, does not enter into any reaction with the reactants,
reagents or solvents involved in the reaction or the products which
form.
[0430] If the polymerization is conducted in the presence of a
solvent, it is selected from the solvents S1) described above.
[0431] For preparation of the polymers, the monomers can be
polymerized with the aid of free radical-forming initiators, also
referred to hereinafter as free-radical initiators or initiators.
Useful free-radical initiators for the free-radical polymerization
are in principle all free-radical initiators which are essentially
soluble in the reaction medium as exists at the time when they are
added and have sufficient activity to initiate the polymerization
at the given reaction temperatures. It is possible to introduce one
individual free-radical initiator or a combination of at least two
free-radical initiators into the process of the invention. In the
latter case, the at least two free-radical initiators can be used
in a mixture or preferably separately, simultaneously or
successively, for example at different times in the course of the
reaction.
[0432] Free-radical initiators which may be used for the
free-radical polymerization are the peroxo and/or azo compounds
customary for the purpose, for example hydrogen peroxide, alkali
metal or ammonium peroxodisulfates (for example sodium
peroxodisulfate), diacetyl peroxide, dibenzoyl peroxide, succinyl
peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate,
tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate,
tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxymaleate,
cumene hydroperoxide, diisopropyl peroxydicarbamate, bis(o-tolyl)
peroxide, didecanoyl peroxide, dioctanoyl peroxide, tert-butyl
peroctoate, dilauroyl peroxide, tert-butyl perisobutyrate,
tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl
hydroperoxide, 2,2'-azobisisobutyronitrile,
2,2'-azobis(2-amidinopropane) dihydrochloride
(=azobis(2-methylpropionamidine) dihydrochloride),
azobis(2,4-dimethylvaleronitrile) or
2,2'-azobis(2-methylbutyronitrile).
[0433] Also suitable are initiator mixtures or redox initiator
systems, for example
[0434] ascorbic acid/iron(II) sulfate/sodium peroxodisulfate,
[0435] tert-butyl hydroperoxide/sodium disulfite,
[0436] tert-butyl hydroperoxide/sodium hydroxymethanesulfinate,
[0437] H.sub.2O.sub.2/Cu.sup.I.
[0438] In the process of the invention, the amount of initiator
system (initiator) used varies within the range from 0.01 to 10
pphm, preferably within the range from 0.1 to 5 pphm, more
preferably within the range from 0.2 to 2 pphm and especially
within the range from 0.3 to 1.5 pphm (parts per hundred
monomer=parts by weight per hundred parts by weight of
monomer).
[0439] In the process of the invention, the free-radical initiator
is generally provided in the form of a solution in a solvent
comprising at least one of the aforementioned solvents S1) and
optionally additionally at least one polyether of polyether
component PE).
[0440] The polymerization can be effected without using a chain
transfer agent (polymerization chain transfer agent) or in the
presence of at least one chain transfer agent. Chain transfer
agents generally refer to compounds having high transfer constants
which accelerate chain transfer reactions and hence bring about a
reduction in the degree of polymerization of the resulting
polymers. The chain transfer agents can be divided into mono-, bi-
and polyfunctional chain transfer agents, according to the number
of functional groups in the molecule that can lead to one or more
chain transfer reactions. Suitable chain transfer agents are
described in detail, for example, by K. C. Berger and G. Brandrup
in J. Brandrup, E. H. Immergut, Polymer Handbook, 3rd edition, John
Wiley & Sons, New York, 1989, pp. 11/81-11/141.
[0441] Suitable chain transfer agents are, for example, aldehydes
such as formaldehyde, acetaldehyde, propionaldehyde,
n-butyraldehyde, isobutyraldehyde.
[0442] Further usable chain transfer agents are formic acid and
salts or esters thereof, such as ammonium formate,
2,5-diphenyl-1-hexene, hydroxyammonium sulfate and hydroxyammonium
phosphate.
[0443] Further suitable chain transfer agents are allyl compounds,
for example allyl alcohol, functionalized allyl ethers, such as
allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl
ether.
[0444] Chain transfer agents used are preferably compounds
comprising sulfur in bound form. Compounds of this kind are, for
example, inorganic hydrogensulfites, disulfites and dithionites or
organic sulfides, disulfides, polysulfides, sulfoxides and
sulfones. These include di-n-butyl sulfide, di-n-octyl sulfide,
diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl
disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl
disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl
sulfoxide, dialkyl sulfide, dialkyl disulfide and/or diaryl
sulfide. Also suitable as polymerization chain transfer agents are
thiols (compounds which comprise sulfur in the form of SH groups,
also referred to as mercaptans). Preferred chain transfer agents
are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols
and/or mercaptocarboxylic acids. Examples of these compounds are
allyl thioglycolates, ethyl thioglycolate, cysteine,
2-mercaptoethanol, 1,3-mercaptopropanol,
3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic
acid, 3-mercaptopropionic acid, mercaptosuccinic acid,
thioglycerol, thioacetic acid, thiourea and alkyl mercaptans such
as n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan.
Examples of bifunctional chain transfer agents which comprise two
sulfur atoms in bonded form are bifunctional thiols, for example
dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic
acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropane,
dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene
glycol bisthioglycolates and butanediol bisthioglycolate. Examples
of polyfunctional chain transfer agents are compounds which
comprise more than two sulfurs in bound form. Examples thereof are
trifunctional and/or tetrafunctional mercaptans.
[0445] The chain transfer agent is more preferably selected from
mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid,
ethylhexyl thioglycolate and sodium hydrogensulfite.
[0446] Preferred chain transfer agents are also hypophosphorous
acid (phosphinic acid) and salts of hypophosphorous acid. A
preferred salt of hypophosphorous acid is the sodium salt.
[0447] If a chain transfer agent is used in the process of the
invention, the amount is typically 1 to 40 pphm ("parts per hundred
monomer", i.e. parts by weight based on one hundred parts by weight
of monomer composition). Preferably, the amount of chain transfer
agents used in the process of the invention is in the range from 3
to 30 pphm, more preferably in the range from 5 to 25 pphm. It is
also possible to conduct the polymerization without adding a chain
transfer agent.
[0448] Typically, the chain transfer agent is added continuously to
the polymerization mixture in its entirety via one of the feeds in
step B2). However, it is also possible to add the chain transfer
agent either in its entirety to the initial charge, i.e. before the
actual polymerization, or to include only some of the chain
transfer agent in the initial charge and to add the remainder
continuously to the polymerization mixture in step B2) via one of
the feeds. The chain transfer agent can be added here in each case
without or with solvent S1).
[0449] The amount of chain transfer agent and the way in which it
is added to the reaction mixture have a major influence on the
average molecular weight of the polymer composition P1). If no
chain transfer agent or only a small amount of chain transfer agent
is used and/or if the addition predominantly precedes the
polymerization, this generally leads to higher average molecular
weights of the polymer formed. If, by contrast, a relatively large
amount of chain transfer agent is used and/or the chain transfer
agent is added for the most part during the polymerization (step
B2)), this generally leads to a smaller average molecular
weight.
[0450] In order to avoid or to reduce unwanted foam formation in
the synthesis, in transport (for example in pumping) and in
storage, and also in film production, defoamers and foam inhibitors
may be used. In principle, all known foam inhibitors or defoamers
are useful. Mention should be made here, for example, of (1)
oil-based systems based on mineral oil or vegetable oil, which may
additionally comprise waxes or silica particles, (2) water-based
systems in which oil and waxes are dispersed, (3) silicone-based
systems (polysiloxanes), for example in water-soluble form, as oil
or water-based emulsion, (4) EO/PO-based polyalkoxylates, (5) alkyl
polyacrylates, (6) fatty acids and fatty acid esters, especially
mono- and diglycerides of fatty acids, (8) fatty alcohol
alkoxylates, (9) defoamers from the class of the phosphoric esters
and salts thereof, such as sodium
(C.sub.6-C.sub.20-alkyl)phosphates, e.g. sodium octylphosphate or
tri(C.sub.1-C.sub.20-alkyl) phosphates, e.g. tributyl phosphate,
and (10) metal soaps, such as aluminum stearate or calcium
oleate.
[0451] The polysiloxanes (polydimethylsiloxanes) can also be used
in modified form, for example in alkyl group-modified or polyether
group-modified form. These are used with preference.
[0452] Preferably, the polymer compositions P1) obtained after the
polymerization has ended (step B3)) are transferred to a suitable
vessel and optionally cooled directly to ambient temperature
(20.degree. C.).
[0453] The polymer compositions P1) obtained in this way are
advantageously suitable for production of multilayer films, for
example for use as a washing or cleaning composition or as a sheath
for a liquid washing or cleaning composition. The production of
multilayer films and of sheaths based thereon is described in
detail hereinafter.
[0454] The weight-average molecular weight M.sub.w of the polymer
composition P1) of the invention was determined by means of gel
permeation chromatography (GPC) in aqueous solution using
neutralized polyacrylic acid as polymer standard. This type of
molecular weight determination covers the components of the polymer
composition P1) which comprise the monomers M1) in copolymerized
form. The polymer composition P1) preferably has a weight-average
molecular weight of 2000 to 100 000 g/mol, preferably of 3000 to 80
000 g/mol.
[0455] The polymer composition P1) has a sufficiently low glass
transition temperature TG suitable for film formation. Preferably,
the polymer compositions P1) have a glass transition temperature TG
in the range from 0 to 80.degree. C., more preferably from 0 to
60.degree. C., especially from 0 to 30.degree. C.
[0456] Prior to use for film production (i.e. before it passes
through a drying operation), the polymer composition P1) preferably
has a content of acid groups of more than 1 mmol/g, more preferably
of more than 1.3 mmol/g. Prior to use for film production, the
polymer composition P1) preferably has a content of acid groups of
not more than 15 mmol/g. Prior to use for film production, the
polymer composition P1) especially has a content of acid groups of
1.5 mmol/g to 10 mmol/g.
[0457] In a preferred embodiment, the acid groups of the polymer
composition P1) of the invention are in non-neutralized form.
[0458] As mentioned at the outset, the multilayer film can be
produced by a lamination method. Lamination methods in which two or
more film layers are bonded to one another over their area are
known to those skilled in the art. Lamination involves pressing two
or more than two films together under elevated pressure and/or at
elevated temperature. As likewise mentioned at the outset, the
multilayer film can also be produced by a wet-on-wet application
method. In addition, the multilayer film can also be produced by
using combinations of the aforementioned production methods and the
application method described hereinafter.
[0459] In a preferred embodiment, the multilayer film is produced
by a process in which at least one free-flowing composition capable
of film formation is applied to a carrier material, wherein the
carrier material and/or the at least one free-flowing composition
comprises or consists of a polymer composition P1) as defined above
and hereinafter.
[0460] The invention further provides a process for producing a
multilayer film as defined above, in which [0461] a1) a first
free-flowing composition capable of film formation is applied to a
carrier material to obtain a first layer, [0462] a2) the first
layer applied to the carrier material is optionally subjected to an
increase in viscosity, [0463] a3) a second free-flowing composition
capable of film formation is applied to the first layer obtained in
step a1) or in step a2) to obtain a second layer, [0464] a4) the
second layer is optionally subjected to an increase in viscosity,
[0465] a5) step a3) is optionally repeated with a further
composition capable of film formation to obtain a further layer and
step a4) is optionally then repeated, it being possible to repeat
steps a3) and a4) once or more than once, [0466] a6) the layers
applied to the carrier material are optionally subjected to a
further increase in viscosity, [0467] a7) the multilayer film
obtained is optionally detached from the carrier material,
[0468] with the proviso that the free-flowing compositions each
comprise a component which is capable of film formation and is
independently selected from at least one polymer composition P1),
at least one polymer P2) or a mixture thereof, and with the proviso
that at least one of the free-flowing compositions and/or the
carrier material comprises or consists of a polymer composition P1)
as defined in any of the preceding claims.
[0469] In a specific embodiment, the application of two or more
than two of the free-flowing compositions can also be effected
partly or fully simultaneously. For this purpose, for example, the
application of the (n+1)th composition can be commenced before the
application of the nth composition has completely ended.
[0470] In a further specific embodiment, the production of the
multilayer film proceeds from a carrier material which already
comprises the first film layer and optionally also already
comprises further film layers of the multilayer film. In other
words, a carrier material which already comprises the first film
layer and optionally further film layers of the multilayer film is
used in step a1). In this case, the carrier material forms part of
the multilayer film and remains in the multilayer film after the
application of all the further layers. This means that the further
layers applied to the carrier material are not subsequently
detached again from the carrier material. In this embodiment, there
is therefore no step a7) of the above-described process.
[0471] The viscosity of the free-flowing composition is matched to
the technical demands of the production method and is determined by
factors including the concentration of the components capable of
film formation, the solvent content (water), the additives added
and the temperature.
[0472] The free-flowing compositions capable of film formation are
applied in steps a1), a3) and a5) generally by means of standard
methods, for example by means of methods selected from airblade
coating, knife coating, airknife coating, squeegee coating,
impregnation coating, dip coating, reverse roll coating, transfer
roll coating, gravure coating, kiss coating, flow coating, cascade
flow coating, slide coating, curtain coating, mono- and
multilaminar slot die coating, spray coating, spin coating, or
printing methods such as relief printing, intaglio printing,
rotogravure printing, flexographic printing, offset printing,
inkjet printing, letterpress printing, pad printing, heatseal
printing or screenprinting methods. The application can also be
continuous or semicontinuous, for example when the carrier material
is moving, for example a permanently or intermittently moving
belt.
[0473] Suitable carrier materials are firstly all materials which
enable simple detachment of the finished multilayer film. Examples
of these include glass, metals such as galvanized steel sheet or
stainless steel, polymers such as silicones or polyethylene
terephthalate, polymer-coated paper, such as silicone paper, etc.
Suitable carrier materials are secondly monolaminar or multilaminar
polymer films which remain as film layers in the multilayer film of
the invention. With regard to the composition of these carrier
materials, reference is made to the disclosure relating to polymer
compositions P1) and polymers P2).
[0474] The increase in viscosity in layers a2), a4) and a6) can be
effected by means of standard methods and generally depends on the
form in which the free-flowing compositions capable of film
formation have been applied in steps a1), a3) and a5). If they have
been applied as a melt, for example, there is generally already an
increase in viscosity in the course of cooling. The cooling can be
effected by simply leaving the carrier material to stand or by
active cooling, such as cooling of the carrier material, jetting
with a cool gas (jet), cooling in a cold room/refrigerator and the
like. If the free-flowing composition capable of film formation has
been applied in the form of a solution or dispersion, it is
generally necessary to remove at least some of the solvent, which
can be effected, for example, by simply leaving the carrier
material to stand, drying with an air jet or hot air jet, drying in
drying cabinets, heating of the carrier material, application of a
reduced pressure, optionally with simultaneous supply of heat, IR
irradiation, microwave radiation, for example in a corresponding
oven, and the like. Should the composition be curable, for example
because the polymers present therein comprise as yet unconverted
polymerizable/condensable groups, the increase in viscosity can
alternatively or additionally be effected by curing the polymer.
The measures suitable for curing depend on the
polymerizable/condensable groups present. For instance,
ethylenically unsaturated crosslinkable groups are especially cured
by UV radiation; condensable groups, by contrast, generally cure
either by being left to stand or with supply of heat. The heat can
again be supplied as described above, i.e., for example, by
incidence of warm or hot air or other warm or hot gases, drying in
drying cabinets, heating of the carrier material, IR irradiation
and the like. It is also possible to gelate the solution or
dispersion applied by cooling, in the sense of forming a physical
network extended over macroscopic dimensions, which likewise
results in an increase in viscosity.
[0475] In a specific embodiment, the free-flowing compositions
capable of film formation for two or more than two of the layers
that form the multilayer film are applied by a wet-on-wet
application method. The application in a3), a5) etc. can thus be
effected wet-on-wet, meaning that the next layer can also be
applied to the layer applied in step a1), a3) and/or a5) without an
explicit step for increasing viscosity having been conducted
beforehand. This is especially true when the layer to which the
next polymer layer is applied is sufficiently thin, such that it
solidifies sufficiently even without being explicitly left to
stand, dried, heated, cured, etc. before the next layer is applied,
and there is no complete mixing with the components of the next
layer. This is also true when the two layers, i.e. those to which
application is effected, and the layer applied subsequently do not
have any strong tendency to mix, for example because one layer is
based on an aqueous polymer solution/dispersion and the other on a
hydrophobic organic solution/dispersion or a hydrophobic melt.
[0476] The polymers applied in steps a1), a3), a5) etc. are
film-forming polymers.
[0477] In a particular embodiment, after steps a1), a2), a3), a4),
a5) and/or a6), it is also possible to apply one or more layers
that do not comprise any film-forming polymers. These are
especially layers comprising components (functional materials)
connected to the desired end use of the multilayer film. Should the
film serve, for example, in or as a washing composition or as a
sheath for washing compositions, these optional further layers may
comprise surfactants, builders, cobuilders, bleaches, enzymes,
enzyme stabilizers, graying inhibitors, optical brighteners,
fragrances, bitter substances, dyes, etc. These components may,
like the polymer layers too, be applied in solution/dispersion or
melt. Suitable application techniques here too are those mentioned
above.
[0478] The application of these layers may also be followed by a
step of increasing the viscosity, or the next layer can be applied
wet-on-wet. The statements made above apply analogously.
[0479] If the above-described layers that are applied do not
comprise any film-forming polymers but do comprise components
connected to the desired end use of the multilayer film, it is
possible after steps a1), a2), a3), a4), a5) and/or a6), especially
after steps a1), a3) and/or a5), to emboss or punch the polymer
layer, so as to give rise to recesses in which the functional
materials applied at a later stage can be accommodated in
relatively large amounts. This can be effected by means of standard
embossing, printing, stamping and punching tools.
[0480] The process of the invention allows the production of
multilayer films without a complex lamination method in which the
individual films have to be bonded to one another. It will be
appreciated that the multilayer films of the invention can also be
produced, as described above, by bonding two or more than two film
layers to one another by laminating. For instance, multilaminar
polymer films which serve as carrier material for application of
further film layers may be provided by bonding two or more than two
film layers to one another by laminating.
[0481] For provision of the compositions applied in steps a1), a3),
a5) etc., for example, a component which is capable of film
formation and is selected from at least one polymer composition
P1), at least one polymer P2) or a mixture thereof, optionally
after addition of at least one additive, is melted or dissolved in
a suitable solvent or solvent mixture, the free-flowing composition
thus obtained is poured out to form a layer and the solvent or
solvent mixture is optionally removed by evaporation.
[0482] Suitable solvents and solvent mixtures are those described
above as component S1), to which reference is made here in its
entirety. The solvent is more preferably selected from water,
ethanol, n-propanol, isopropanol, ethylene glycol, diethylene
glycol, 1,2-propylene glycol, 1,2-dipropylene glycol and mixtures
thereof. In a specific embodiment, the solvent used is selected
from water and a mixture of water and at least one solvent other
than water, selected from ethanol, n-propanol, isopropanol,
ethylene glycol, diethylene glycol, 1,2-propylene glycol,
1,2-dipropylene glycol and mixtures thereof.
[0483] In a specific embodiment of the present invention, a first
dilaminar film is combined with a second dilaminar film in the
manner of a lamination.
[0484] Preferably, the first dilaminar film comprises a layer S1)
comprising a polymer composition P1) or consisting of a polymer
composition P1) and a layer S2) comprising at least one polymer P2)
or consisting of at least one polymer P2). The first dilaminar film
may be combined with a second dilaminar film by steps a1) to a4),
optionally after the drying of the second layer, in the manner of a
lamination.
[0485] The second dilaminar film may likewise be produced
simultaneously according to steps (a) to (d), as described above,
or in a plant connected in parallel. If the same composition is
used for the laminas of the two films that come into contact, the
multilaminar film produced in this way via lamination consists of
three laminas. In that case, if the outer laminas are chemically
different, the resulting multilayer film has three chemically
different laminas. If the outer laminas are also chemically
identical, the resulting multilayer film has only two chemically
different laminas.
[0486] In a further embodiment of the present invention, a
dilaminar film is cut into two halves and then the two halves of
the film obtained are laminated. When a customary machine for
production of film sheets is used, these can be cut in the middle
in machine direction, placed one on top of the other and then
laminated. In this embodiment too, the dilaminar film can be
produced by steps a1) to a4) and optionally drying of the second
layer. In this embodiment, it is also possible to laminate the
chemically identical interfaces to one another in order to
effectively obtain a multilayer film composed of three laminas,
where the two outer laminas are chemically identical.
[0487] The advantage of the two abovementioned embodiments of the
present invention is that of distinctly accelerated drying by
virtue of the reduced layer thickness, which is directly connected
to an elevated production rate. Without being restricted to the
theory, the mass transfer of the solvent through the film with a
constant coefficient of diffusion is proportional to 1/film
thickness.
[0488] A specific embodiment is a process for producing a
multilayer film of the invention comprising at least one additive.
In this case, an individual layer or a plurality of but not all the
layers or all the layers may each comprise one or more than one
additive. Alternatively or additionally, it is possible that at
least one additive is present between at least two layers.
Additives may, as described above, already be added in the course
of the free-radical polymerization in step B) or in the provision
of the free-flowing compositions capable of film formation in steps
a1), a3), a5) etc. Whether the addition is already effected in step
B) or only in the provision of the free-flowing compositions
capable of film formation depends on the nature and effect of the
particular additive.
[0489] The additives may be auxiliaries for adjustment of the
properties of the free-flowing compositions capable of film
formation, typical additives for the end use of the multilayer
films or mixtures thereof. Typical additives for the end use of the
multilayer films are especially selected from additives for washing
compositions, cleaning compositions, dishwashing compositions,
rinse aids, hygiene products, disinfectants, personal care
compositions, personal cleansing compositions, cosmetic
compositions, pharmaceutical compositions, crop protection
compositions, bait traps, wetting agents, etc.
[0490] Preference is given to multilayer films in which at least
one of the layers includes an additive. Particular preference is
given to multilayer films in which at least one of the layers
includes an additive which is a constituent customary for washing
and cleaning compositions. In that case, the additive is preferably
selected from nonionic, anionic, cationic and amphoteric
surfactants, builders, complexing agents such as
methylglycinediacetic acid, glutaminediacetic acid, glutamic acid
diacetic acid and citric acid and the sodium and potassium salts
thereof, bleaches, enzymes, enzyme stabilizers, bases, corrosion
inhibitors, defoamers and foam inhibitors, wetting agents, dyes,
pigments, fragrances, fillers, tableting aids, disintegrants,
thickeners, solubilizers, organic solvents, electrolytes, pH
modifiers, perfume carriers, bitter substances, fluorescers,
hydrotropes, antiredeposition agents, optical brighteners, graying
inhibitors, antishrink agents, anticrease agents, dye transfer
inhibitors, antimicrobial active ingredients, antioxidants,
anti-yellowing agents, corrosion inhibitors, antistats, ironing
aids, hydrophobizing and impregnating agents, antiswell and
antislip agents, plasticizers, scavengers, polymers other than the
polymer compositions P1) and the polymers P2), agents for
modification of gas permeability and water vapor permeability,
antistats, glidants, slip agents, UV absorbers and mixtures
thereof.
[0491] In a preferred embodiment, a layer of the multilayer film of
the invention comprises, as additive, at least one enzyme and
optionally at least one enzyme stabilizer. Suitable enzymes and
enzyme stabilizers are those mentioned hereinafter as components
E1).
[0492] Suitable bitter substances are those mentioned hereinafter
as components E6).
[0493] Some additives can fulfill more than one function, for
example as solvent S1) and as plasticizer.
[0494] In order to make the multilayer films of the invention more
flexible, plasticizers can be added thereto in the course of
production. For production of the free-flowing compositions capable
of film formation, preferably 0.5% to 30% by weight, more
preferably 2% to 20% by weight and especially 3% to 15% by weight
of plasticizer is used, based on the total weight of the
composition.
[0495] Suitable plasticizers are alkyleneamines, alkanolamines,
polyols such as alkylene glycols and oligoalkylene glycols, e.g.
2-methylpropane-1,3-diol, 3-methylpentane-1,5-diol,
hydroxypropylglycerol, neopentyl glycol, alkoxylated glycerol (for
example Voranol.RTM. from Dow Chemicals), water-soluble
polyesterpolyols (for example TriRez from Geo Specialty Chemicals)
and mixtures thereof. Suitable plasticizers are also
polyetherpolyols available under the Lupranol.RTM. name from BASF
SE. The term "alkyleneamines" refers to condensation products of
alkanolamines with ammonia or primary amines; for example,
ethyleneamines are obtained by reaction of monoethanolamine with
ammonia in the presence of a catalyst. This results in the
following main components: ethylenediamine, piperazine,
diethylenetriamine and aminoethylethanolamine.
[0496] Preferably, the plasticizers are selected from glycerol,
diglycerol, propylene glycols having a weight-average molecular
weight of up to 400, ethylene glycol, polyethylene glycols having a
weight-average molecular weight of up to 400, diethylene glycol,
triethylene glycol, tetraethylene glycol, sugar alcohols such as
sorbitol, mannitol, xylitol, isomalt, lactitol, isopentyldiol,
neopentyl glycol, trimethylolpropane, diethylenetriamine,
triethylenepentamine, triethanolamine and mixtures thereof.
[0497] In order to make the multilayer films of the invention more
resistant to aggressive ingredients (for example chlorine-releasing
compounds as used in the field of disinfection of water, etc.), it
is possible to add what are called "scavengers" (capture molecules)
to the film. Suitable scavengers are polyamines, polymeric
polyamines, such as polyethyleneimines, poly(amidoamines) and
polyamides. In addition, it is also possible to use ammonium
sulfate, primary and secondary amines having a low vapor pressure,
such as ethanolamines, amino acid and salts thereof, and also
polyamino acid and salts thereof, fatty amines, glucosamines and
other aminated sugars. It is further possible to use reducing
agents, such as sulfites, bisulfites, thiosulfites, thiosulfates,
iodides, nitrites and antioxidants such as carbamates, ascorbates
and mixtures thereof.
[0498] For production of the multilayer films of the invention, it
is possible to add further additives in the form of polymers to the
polymer composition P1) and/or the polymers P2) before and/or
during the film production. Typically, 0.05% to 20% by weight,
preferably 0.1% to 15% by weight and more preferably 0.2% to 10% by
weight of polymers (based on the total weight of the polymer
composition P1), polymers P2) and additional polymers) are used.
Such additives can simultaneously improve the washing properties of
the multilayer film, improve the mechanical properties of the
multilayer film, and increase the resistance of the multilayer film
to washing composition components. Suitable further polymers are,
for example, oligosaccharides and polysaccharides, starch, degraded
starches (maltodextrins), cellulose ethers, specifically
hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose,
ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl
ethyl cellulose, microcrystalline cellulose, inulin,
carboxymethylcellulose, for example in the form of the sodium
salts, alginic acid and alginates, pectin acid and pectins,
polyethyleneimines, alkoxylated and especially ethoxylated
polyethyleneimines, graft polymers of vinyl acetate onto
polyalkylene glycols, especially onto polyethylene glycols,
homopolymers of N-vinylpyrrolidone, copolymers of
N-vinylpyrrolidone and N-vinylimidazole, copolymers of
N-vinylpyrrolidone with vinyl acetate and with vinylcaprolactam,
polyalkylene oxides, polyvinyl alcohol, polyvinyl alcohols with
fractions of unhydrolyzed vinyl acetate, thickeners, for example
xanthan gum, guar gum, gelatin, agar-agar and mixtures thereof.
[0499] It is additionally possible to subject at least one surface
or both surfaces of the multilayer films of the invention to at
least partial coating with at least one additive.
[0500] Such a treatment may serve, for example, to provide the
surface with particular properties, such as nonstick action,
antistatic action, hydrophilic or hydrophobic properties, etc. It
is thus possible to provide the multilayer films, for example, with
better detachment properties from the carrier material used in the
production, better roll-off properties, better glide properties,
reduced tack, better compatibility with particular components
ensheathed or coated therewith, etc. According to the nature and
formulation of the additive, the application can be effected by
standard methods, for example by spraying, dipping, powder
application, etc. Suitable additives for coating of the surface of
the multilayer films of the invention are, for example, talc,
surfactants such as silicone-containing surfactants, waxes,
etc.
[0501] Printing or embossing of the multilayer films of the
invention is also possible, in order to provide these, for example,
with patterns, motifs, or inscriptions. The printing may follow the
production of the multilayer film or be effected in an intermediate
step during the buildup of the layers. This printing step
preferably follows directly inline after the film production, in a
separate printing or converting process, or inline with the pod
production. Suitable printing methods are inkjet printing, and also
intaglio and planographic printing methods such as flexographic
printing, gravure printing, offset printing or inkjet printing.
[0502] As stated above, the film production process is not subject
to any particular restrictions and the person skilled in the art is
able to apply any desired production process of which he is aware
on account of his art knowledge. This applies to the production of
multilayer films which are to be used as such for use as a washing
composition or as a cleaning composition. The same applies to the
production of sheaths and coatings based on a multilayer film of
the invention. Particularly suitable methods are coating bar
methods, casting methods, roll application methods and extrusion
methods.
[0503] The multilayer films of the invention are generally
thermoplastic and can be subjected to a forming operation by
thermoforming (i.e. hot forming, deep drawing or vacuum deep
drawing). A process for producing water-soluble film packagings by
a thermoforming process which comprises a hot forming or deep
drawing step is described in WO 00/55044.
[0504] For production of film portions, the multilayer film of the
invention can be processed in a suitable manner, for example by
cutting to a desired size and/or folding to form compartments.
Subsequently, the edges can be sealed by standard sealing methods
such as heat sealing, liquid sealing or pressure sealing.
[0505] As stated above, the multilayer film of the invention may
preferably consist of 2 to 20 layers, more preferably 2 to 15
layers and especially 2 to 10 layers. These specifically include
multilayer films consisting of 2, 3, 4, 5, 6, 7 or 8 layers. The
sequence of the layers of the multilayer films of the invention is
guided by the desired end use.
[0506] According to the invention, one or more layers of the
multilayer film of the invention comprise a polymer composition
P1). In a specific embodiment, one layer of the multilayer film of
the invention consists of a polymer composition P1).
[0507] In a preferred embodiment, one or more layers of the
multilayer film of the invention comprise a homo- or copolymer P2)
comprising repeat units which derive from vinyl alcohol, vinyl
esters or mixtures thereof. Preferred polymers P2) are polyvinyl
alcohols having a hydrolysis level of 50 to 99 mol %, more
preferably of 70 to 98 mol %.
[0508] In a specific embodiment, one or more layers of the
multilayer film of the invention comprise a cold water-soluble
polyvinyl alcohol P2) having a hydrolysis level of not more than 90
mol %.
[0509] In a further specific embodiment, one or more layers of the
multilayer film of the invention comprise a hot water-soluble
polyvinyl alcohol P2) having a hydrolysis level of about 90 to
about 99 mol %.
[0510] In a further preferred embodiment, one or more layers of the
multilayer film of the invention comprise at least one cellulose
ether P2). Preferred cellulose ethers are selected from alkyl
celluloses, hydroxyalkyl celluloses, hydroxyalkyl alkyl celluloses,
carboxyalkyl celluloses and salts thereof, carboxyalkyl alkyl
celluloses and salts thereof, carboxyalkyl hydroxyalkyl celluloses
and salts thereof, carboxyalkyl hydroxyalkyl alkyl celluloses and
salts, sulfoalkyl celluloses and salts thereof. Particularly
preferred cellulose ethers are selected from carboxymethyl
celluloses. The carboxyalkyl radicals may also be in salt form.
[0511] In a further preferred embodiment, one or more layers of the
multilayer film of the invention comprise at least one homo- or
copolymer comprising at least one copolymerized monomer selected
from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole,
2-vinylpyridine, 4-vinylpyridine, salts of the three latter
monomers, vinylpyridine N-oxide, N-carboxymethyl-4-vinylpyridium
halides and mixtures thereof.
[0512] In a specific embodiment, one or more layers of the
multilayer film of the invention comprise a polyvinylpyrrolidone
homopolymer.
[0513] In a further specific embodiment, one or more layers of the
multilayer film of the invention comprise a copolymer comprising
copolymerized vinylpyrrolidone and vinylimidazole.
[0514] Washing, Cleaning and Dishwashing Compositions
[0515] The multilayer films of the invention are suitable as such
for use as a washing composition or as a cleaning composition or as
a dishwashing composition. The term "dishwashing composition" here
also covers rinse aids. Since at least one layer of the multilayer
films includes a polymer composition P1), they feature dispersing,
film-inhibiting, emulsifying and/or surfactant properties, and so
the polymer composition P1) also contributes to the washing and
cleaning performance. The multilayer films of the invention do not
just improve the washing power, i.e. actively help to remove soil
from the fabric or from hard surfaces such as ceramic, glass,
plastic and metal, but also prevent redeposition of detached soil
on concomitantly washed fabric or hard surfaces, meaning that they
have a graying-inhibiting and deposition-inhibiting effect. Because
of their washing and cleaning effect, they are especially suitable
for formulation of laundry detergents and dishwashing compositions.
In this embodiment too, the multilayer films of the invention take
the form of a self-supporting flat structure having at least two
film layers.
[0516] The maximum thickness of the multilayer films of the
invention for use as a washing composition or as a cleaning
composition or as a dishwashing composition is preferably not more
than 30 mm, more preferably not more than 20 mm and especially not
more than 15 mm.
[0517] The thickness of the multilayer films for use as a washing
composition or as a cleaning composition or as a dishwashing
composition is preferably less than the length of the greatest
longitudinal axis by a factor of at least 2, more preferably at
least 5 and especially at least 10.
[0518] Preferably, multilayer films for use as a washing
composition or as a cleaning composition or as a dishwashing
composition have an area in the plane of the polymer layers of at
least 1 cm.sup.2, more preferably of at least 2 cm.sup.2,
especially of at least 3 cm.sup.3.
[0519] Preferably, the multilayer films for use as a washing
composition or as a cleaning composition or as a dishwashing
composition have an area in the plane of the polymer layers of 1 to
500 cm.sup.2, more preferably of 2 to 400 cm.sup.2, especially of 3
to 300 cm.sup.2.
[0520] Preferably, the multilayer films for use as a washing
composition or as a cleaning composition or as a dishwashing
composition have a volume of 1 to 100 cm.sup.3, more preferably of
2 to 80 cm.sup.3, especially of 3 to 60 cm.sup.3.
[0521] The outer shape of the multilayer films for use as a washing
composition or as a cleaning composition or as a dishwashing
composition is generally uncritical. Suitable structures are those
having an essentially round, elliptical or rectangular footprint.
For aesthetic reasons, it is also possible to choose other shapes,
such as leaves, flowers, animals, etc.
[0522] The multilayer films of the invention are advantageously
also suitable for use for packaging of washing, cleaning and
dishwashing compositions as portions. They are firstly specifically
suitable for production of a sheath comprising washing, cleaning or
dishwashing compositions in solid or liquid or gel form or at least
one of the components thereof. The multilayer films of the
invention are additionally suitable for production of a coating on
a solid washing, cleaning or dishwashing composition or on at least
one solid component thereof. The multilayer films dissolve at the
start of the respective use (for example in the washing or rinse
water), thus release the constituents of the washing and cleaning
composition and, in dissolved form, because of their dispersing,
film-inhibiting, emulsifying and surfactant properties, contribute
considerably to the washing and cleaning performance. The
multilayer films of the invention do not just improve the washing
power, i.e. actively help to remove soil from the fabric or from
hard surfaces such as ceramic, glass, plastic and metal, but also
prevent (re)deposition of detached soil and sparingly soluble salts
of the water hardness ions on concomitantly washed fabric or hard
surfaces, meaning that they have a graying-inhibiting and
deposition-inhibiting effect. They especially prevent the
redeposition of particulate soil, for example clay particles, soot
particles and color pigments, and the deposition of sparingly
soluble salts of the water hardness ions, such as the carbonates
and silicates of calcium(II) and magnesium (II) ions. Because of
their washing effect, they are especially suitable for formulation
of laundry detergents.
[0523] The washing or cleaning composition portions of the
invention comprise, as sheath and/or coating, at least one washing-
or cleaning-active multilayer film of the invention. The layers of
the multilayer film may comprise washing-active or cleaning-active
components as additives. In addition, the washing or cleaning
composition portions of the invention comprise measured amounts of
at least one washing-active or cleaning-active composition within
the sheath or coating. It is possible here that the washing
composition or cleaning composition portions comprise just one
individual washing- or cleaning-active composition. It is also
possible that the washing composition or cleaning composition
portions of the invention comprise two or more than two different
washing- or cleaning-active compositions. The different
compositions may be surrounded by the same or different sheath
and/or coating. In this case, at least one of the sheaths and/or
coatings comprises a washing- or cleaning-active multilayer film of
the invention. The different compositions may differ with regard to
the concentration of the individual components (in quantitative
terms) and/or with regard to the nature of the individual
components (in qualitative terms). It is more preferable that the
components, in terms of type and concentration, are matched to the
tasks that the active ingredient portion packages have to fulfill
in the washing or cleaning operation.
[0524] The multilayer films of the invention are also
advantageously suitable for production of what are called
multichamber systems. Multichamber systems have 2, 3, 4, 5 or more
than 5 chambers which each comprise a single component or a
plurality of components of a washing or cleaning composition. This
may in principle be a single washing- or cleaning-active
ingredient, a single auxiliary or any desired mixture of two or
more than two active ingredients and/or auxiliaries. The
constituents of the individual chambers may each be in liquid, gel
or solid form. Multichamber systems are an option, for example, in
order to separate components of a washing or cleaning composition
that are incompatible or not very compatible from one another. For
example one chamber may comprise one or more enzyme(s) and another
chamber at least one bleach. Multichamber systems are also an
option, for example, in order to facilitate controlled release of a
particular component, for example at a certain time point in the
washing or cleaning operation. For this purpose, for example, it is
possible to use film materials of different material thickness. In
addition, individual chambers can be produced using a multilayer
film of the invention and others using a different conventional
film.
[0525] Where statements are made hereinafter regarding the
qualitative and quantitative composition of washing and cleaning
compositions, these shall always encompass the overall formulation
composed of multilayer film and ensheathed or coated components. In
the case of formulation of this composition as a multichamber
system, the chambers may each comprise an individual component or a
plurality of components of the formulation, or the total amount of
any component may be divided between two or more than two
chambers.
[0526] The washing composition or cleaning composition or
dishwashing composition portions of the invention comprise at least
one washing- or cleaning-active composition within. These
compositions may be any desired substances or substance mixtures
that are of relevance in connection with a washing or cleaning
operation. These are primarily the actual washing compositions or
cleaning compositions with their individual components explained in
detail hereinafter.
[0527] In the context of the present invention, washing
compositions are understood to mean those compositions which are
used for cleaning of flexible materials having high absorptivity,
for example of materials having a textile character, whereas
cleaning compositions in the context of the present invention are
understood to mean those compositions which are used for cleaning
of materials having a closed surface, i.e. having a surface which
has only few small pores, if any, and as a result has only low
absorptivity, if any.
[0528] Examples of flexible materials having high absorptivity are
those which comprise or consist of natural, synthetic or
semisynthetic fiber materials and which accordingly generally have
at least some textile character. The fibrous materials or those
consisting of fibers may in principle be in any form that occurs in
use or manufacture and processing. For example, fibers may be in
unordered form in the form of staple or aggregate, in ordered form
in the form of fibers, yarns, threads, or in the form of
three-dimensional structures such as nonwoven fabrics, lodens or
felt, woven fabrics, knitted fabrics, in all conceivable binding
types. The fibers may be raw fibers or fibers in any desired stages
of processing. Examples are natural protein or cellulose fibers,
such as wool, silk, cotton, sisal, hemp or coconut fibers, or
synthetic fibers, for example polyester, polyamide or
polyacrylonitrile fibers.
[0529] Examples of materials having only few and small pores, if
any, and having zero or only low absorptivity are metal, glass,
enamel or ceramic. Typical objects made of these materials are, for
example, metallic sinks, cutlery, glass and porcelain dishware,
bathtubs, washbasins, tiles, flags, cured synthetic resins, for
example decorative melamine resin surfaces on kitchen furniture or
painted metal surfaces, for example refrigerators and car bodies,
printed circuit boards, microchips, sealed or painted woods, e.g.
parquet or wall cladding, window frames, doors, plastics coverings
such as floor coverings made of PVC or hard rubber, or rigid or
flexible foams having substantially closed surfaces.
[0530] Examples of cleaning compositions which may comprise the
washing- and cleaning-active multilayer film of the invention
include washing and cleaning compositions, dishwashing compositions
such as manual dishwashing compositions or machine dishwashing
compositions (=dishwashing composition for the machine dishwasher),
metal degreasers, glass cleaners, floor cleaners, all-purpose
cleaners, high-pressure cleaners, neutral cleaners, alkaline
cleaners, acidic cleaners, spray degreasers, dairy cleaners,
commercial kitchen cleaners, machinery cleaners in industry,
especially the chemical industry, cleaners for carwashing and also
domestic all-purpose cleaners.
[0531] The washing, cleaning or dishwashing compositions of the
invention may be compositions comprising a polymer composition P1)
of the invention in the sheath or coating. The washing, cleaning or
dishwashing compositions of the invention may also be portions of
washing or cleaning compositions in solid, liquid or gel form
packaged in pouches. In a specific embodiment, these are called
pouches (liquid tabs). The products may also be compressed shaped
bodies such as tablets ("tabs"), blocks, briquettes, etc. In a
specific embodiment, they are tableted washing or cleaning
compositions. In a further particularly preferred embodiment, they
are then tableted dishwashing compositions, especially tableted
machine dishwashing compositions.
[0532] Tableted dishwashing compositions may be simple tabs or else
what are called "2 in 1", "3 in 1", "5 in 1" or "7 in 1" products
(multifunctional products). Further details of these formulations
can be found in Hermann G. Hauthal, G. Wagner (eds.),
Reinigungs-und Pflegemittel im Haushalt [Domestic Cleaning and Care
Products], Verlag fur chemische Industrie, H. Ziolkowsky GmbH,
Augsburg 2003, Chapter 4.2, pages 161-184. "2 in 1" products
comprise, as well as the customary constituents of machine
dishwashing compositions, additionally a rinse aid. "3 in 1"
products also comprise a water softener. "5 in 1" products
generally also comprise a glass protector and a rinsing power
enhancer. "7 in 1" products also comprise a stainless steel
brightener and a deincrustation agent. In these tableted
dishwashing compositions, the polymer composition P1) of the
invention may be present in the rinse aid core, or it is present in
solid form in the tableted dishwashing composition.
[0533] Washing and Cleaning Compositions
[0534] The washing or cleaning composition of the invention
preferably comprises the following constituents: [0535] A) at least
one sheath and/or coating comprising or consisting of a washing-
and cleaning-active multilayer film of the invention, [0536] B) at
least one surfactant, [0537] C) optionally at least one builder,
[0538] D) optionally at least one bleach system, [0539] E)
optionally at least one further additive, preferably selected from
enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers
and foam inhibitors, dyes, fragrances, fillers, tableting aids,
disintegrants, thickeners, solubilizers, organic solvents,
electrolytes, pH modifiers, perfume carriers, bitter substances,
fluorescers, hydrotropes, antiredeposition agents, optical
brighteners, graying inhibitors, antishrink agents, anticrease
agents, dye transfer inhibitors, antimicrobial active ingredients,
antioxidants, anti-yellowing agents, corrosion inhibitors,
antistats, ironing aids, hydrophobizing and impregnating agents,
antiswell and antislip agents and UV absorbers, and [0540] F)
optionally water.
[0541] In the context of the present invention, the builder C) also
comprises compounds referred to as sequestrant, complexing agent,
chelator, chelating agent or softener.
[0542] The bleach systems D) comprise, as well as bleaches,
optionally also bleach activators, bleach catalysts and/or bleach
stabilizers.
[0543] More preferably, the washing and cleaning composition of the
invention comprises at least one enzyme as additive E).
[0544] A preferred embodiment relates to washing or cleaning
compositions in liquid or gel form, comprising: [0545] A) 0.1% to
20% by weight of at least one sheath and/or coating comprising or
consisting of a washing- and cleaning-active multilayer film of the
invention, [0546] B) 1% to 80% by weight of at least one
surfactant, [0547] C) 0.1% to 50% by weight of at least one
builder, [0548] D) 0% to 20% by weight of a bleach system, [0549]
E) 0.1% to 60% by weight of at least one further additive,
preferably selected from enzymes, enzyme stabilizers, bases,
corrosion inhibitors, defoamers and foam inhibitors, dyes,
fragrances, fillers, tableting aids, disintegrants, thickeners,
solubilizers, organic solvents, electrolytes, pH modifiers, perfume
carriers, bitter substances, fluorescers, hydrotropes,
antiredeposition agents, optical brighteners, graying inhibitors,
antishrink agents, anticrease agents, dye transfer inhibitors,
antimicrobial active ingredients, antioxidants, anti-yellowing
agents, corrosion inhibitors, antistats, ironing aids,
hydrophobizing and impregnating agents, antiswell and antislip
agents and UV absorbers, and [0550] F) 0% to 98.7% by weight of
water.
[0551] The percent by weight data relate to the total weight of the
washing and cleaning composition. The weight amounts of A) to F)
add up to 100% by weight.
[0552] Preferably, the washing or cleaning compositions in liquid
or gel form comprise up to 70% by weight of water, more preferably
up to 50% by weight of water, especially up to 30% by weight of
water.
[0553] A further preferred embodiment relates to solid washing or
cleaning compositions comprising: [0554] A) 0.1% to 20% by weight
of at least one sheath and/or coating comprising or consisting of a
washing- and cleaning-active multilayer film of the invention,
[0555] B) 1% to 50% by weight of at least one surfactant, [0556] C)
0.1% to 70% by weight of at least one builder, [0557] D) 0% to 30%
by weight of a bleach system, [0558] E) 0.1% to 70% by weight of at
least one further additive, preferably selected from enzymes,
enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam
inhibitors, dyes, fragrances, fillers, tableting aids,
disintegrants, thickeners, solubilizers, organic solvents,
electrolytes, pH modifiers, perfume carriers, bitter substances,
fluorescers, hydrotropes, antiredeposition agents, optical
brighteners, graying inhibitors, antishrink agents, anticrease
agents, dye transfer inhibitors, antimicrobial active ingredients,
antioxidants, anti-yellowing agents, corrosion inhibitors,
antistats, ironing aids, hydrophobizing and impregnating agents,
antiswell and antislip agents and UV absorbers, and [0559] F)
optionally water.
[0560] The percent by weight data relate to the total weight of the
washing and cleaning composition. The weight amounts of A) to F)
add up to 100% by weight.
[0561] Component A) With regard to suitable and preferred washing-
and cleaning-active multilayer films of the invention, reference is
made to the details above.
[0562] Component B)
[0563] The washing and cleaning compositions of the invention
comprise at least one surfactant as component B). Suitable
surfactants B) are nonionic, anionic, cationic or amphoteric
surfactants.
[0564] Examples of surfactants B) which may be used in the context
of the present invention include nonionic surfactants (NIS).
Nonionic surfactants used are preferably alkoxylated alcohols.
Preference is given to alkoxylated primary alcohols. Preferred
alkoxylated alcohols are ethoxylated alcohols having preferably 8
to 18 carbon atoms in the alkyl radical and an average of 1 to 12
mol of ethylene oxide (EO) per mole of alcohol. The alcohol radical
may be linear or preferably 2-methyl-branched or may comprise
linear and methyl-branched radicals in a mixture, as typically
present in oxo process alcohol radicals. Especially preferred are
alcohol ethoxylates having linear or branched radicals from
alcohols of native or petrochemical origin having 12 to 18 carbon
atoms, for example from coconut alcohol, palm alcohol, tallow
alcohol or oleyl alcohol, and an average of 2 to 8 EO per mole of
alcohol.
[0565] The ethoxylated alcohols are preferably selected from:
[0566] C.sub.12C.sub.14-alcohols with 3 EO, 5 EO, 7 EO or 9 EO,
[0567] C.sub.9C.sub.11-alcohols with 7 EO, [0568] C.sub.13-oxo
process alcohols with 3 EO, 5 EO, 7 EO or 9 EO, [0569]
C.sub.3C.sub.15-alcohols with 3 EO, 5 EO, 7 EO or 9 EO, [0570]
C.sub.12C.sub.18-alcohols with 3 EO, 5 EO, 7 EO or 9 EO and
mixtures thereof, [0571] 2-propylheptanol with 3 EO, 4 EO, 5 EO, 6
EO, 7 EO, 8 EO and 9 EO
[0572] and mixtures of two or more than two of the aforementioned
ethoxylated alcohols.
[0573] A preferred mixture of nonionic surfactants is a mixture of
C.sub.12C.sub.14-alcohol (lauryl alcohol/myristyl alcohol) with 3
EO and C.sub.12C.sub.18-alcohol (lauryl alcohol/myristyl
alcohol/cetyl alcohol/stearyl alcohol) with 7 EO. Preference is
also given to mixtures of short-chain alcohol ethoxylates (e.g.
2-propylheptanol with 7 EO) and long-chain alcohol ethoxylates
(e.g. C.sub.16C.sub.18 with 7 EO).
[0574] The stated ethoxylation levels are statistical averages
(number averages, Mn), which may be an integer or a fraction for a
specific product. Preferred alcohol ethoxylates have a narrowed
homolog distribution (narrow range ethoxylates, NRE). In addition
to these nonionic surfactants, it is also possible to use fatty
alcohols with more than 12 EO. Examples of these are tallow alcohol
with 14 EO, 25 EO, 30 EO or 40 EO. Also usable are nonionic
surfactants comprising ethylene oxide (EO) and propylene oxide (PO)
groups together in the molecule. It is possible here to use block
copolymers with EO-PO block units or PO-EO block units, but also
EO-PO-EO copolymers or PO-EO-PO copolymers. It is of course also
possible to use mixedly alkoxylated nonionic surfactants in which
EO and PO units are not in blocks but in random distribution. Such
products are obtainable by simultaneous action of ethylene oxide
and propylene oxide on fatty alcohols.
[0575] Surfactants suitable as component B) are also polyetherols,
preferably with a number-average molecular weight of at least 200
g/mol.
[0576] Suitable polyetherols may be linear or branched, preferably
linear. Suitable polyetherols generally have a number-average
molecular weight in the range from about 200 to 100 000 g/mol,
preferably 300 to 50 000 g/mol, more preferably 500 to 40 000
g/mol. Suitable polyetherols are, for example, water-soluble or
water-dispersible nonionic polymers having repeat alkylene oxide
units. Preferably, the proportion of repeat alkylene oxide units is
at least 30% by weight, based on the total weight of the compound.
Suitable polyetherols are polyalkylene glycols, such as
polyethylene glycols, polypropylene glycols, polytetrahydrofurans
and alkylene oxide copolymers. Suitable alkylene oxides for
preparation of alkylene oxide copolymers are, for example, ethylene
oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene
oxide. Suitable examples are copolymers of ethylene oxide and
propylene oxide, copolymers of ethylene oxide and butylene oxide,
and copolymers of ethylene oxide, propylene oxide and at least one
butylene oxide. The alkylene oxide copolymers may comprise the
copolymerized alkylene oxide units in randomly distributed form or
in the form of blocks. Preferably, the proportion of repeat units
derived from ethylene oxide in the ethylene oxide/propylene oxide
copolymers is 40% to 99% by weight. Particular preference is given
to ethylene oxide homopolymers and ethylene oxide/propylene oxide
copolymers.
[0577] In addition, further nonionic surfactants which may be used
are also alkyl glycosides of the general formula (IV)
R.sup.10O(G).sub.i (IV)
[0578] in which [0579] R.sup.10 is a primary straight-chain or
methyl-branched aliphatic radical having 8 to 22 carbon atoms,
[0580] G is a glycoside unit having 5 or 6 carbon atoms, and [0581]
i is any number between 1 and 10.
[0582] In the compounds of the formula (IV), R.sup.10 is preferably
a 2-methyl-branched aliphatic radical having 8 to 22 and preferably
12 to 18 carbon atoms. [0583] G is preferably glucose.
[0584] The oligomerization level i, which states the distribution
of monoglycosides and oligoglycosides, is preferably within a range
from 1.2 to 1.4.
[0585] A further class of nonionic surfactants which are used with
preference in the context of the present invention and are used
either as the sole nonionic surfactant or in combination with other
nonionic surfactants is that of alkoxylated, preferably ethoxylated
or ethoxylated and propoxylated, fatty acid alkyl esters,
preferably having 1 to 4 carbon atoms in the alkyl chain.
Especially preferred are fatty acid methyl esters as described, for
example, in the Japanese patent application JP 58/217598, or those
which are preferably prepared by the process described in the
international patent application WO 90/13533.
[0586] Further suitable nonionic surfactants are amine oxides, for
example N-cocoalkyl-N,N-dimethylamine oxide and
N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid
alkanolamides. These nonionic surfactants are preferably used as a
mixture with alkoxylated alcohols. Preference is given to the
mixture with ethoxylated fatty alcohols.
[0587] The weight amount of these nonionic surfactants is
preferably not more than that of the ethoxylated fatty alcohols,
especially not more than half thereof.
[0588] Further suitable surfactants B) are polyhydroxy fatty acid
amides of the formula (V)
##STR00004##
[0589] in which the R.sup.11--C(.dbd.O) group is an aliphatic acyl
radical having 6 to 22 carbon atoms, R.sup.12 is hydrogen, an alkyl
radical having 1 to 4 carbon atoms or a hydroxyalkyl radical having
1 to 4 carbon atoms, and R.sup.13 is a linear or branched
polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10
hydroxyl groups. The polyhydroxy fatty acid amides are known
substances which can typically be obtained by reductive amination
of a reducing sugar with ammonia, an alkylamine or an alkanolamine
and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a fatty acid chloride. The group of polyhydroxy fatty acid
amides includes in this connection also compounds of the formula
(VI)
##STR00005##
[0590] in which R.sup.14 is a linear or branched alkyl or alkenyl
radical having 7 to 12 carbon atoms, R.sup.15 is a linear, branched
or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene
radical having 6 to 8 carbon atoms, and R.sup.16 is a linear,
branched or cyclic alkyl radical or an aryl radical or an oxyalkyl
radical having 1 to 8 carbon atoms, preference being given to
C.sub.1-C.sub.4-alkyl or phenyl radicals, and R.sup.17 is a linear
polyhydroxyalkyl radical wherein the alkyl chain is substituted by
at least two hydroxyl groups, or alkoxylated, preferably
ethoxylated or propoxylated derivatives of this radical. R.sup.17
is preferably obtained by reductive amination of a sugar, for
example glucose, fructose, maltose, lactose, galactose, mannose or
xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then
be converted to the desired polyhydroxy fatty acid amides, for
example according to WO 95/07331 by reaction with fatty acid methyl
esters in the presence of an alkoxide as catalyst.
[0591] Suitable surfactants B) are also anionic surfactants.
Typical examples of anionic surfactants are soaps, alkylsulfonates,
alkylbenzenesulfonates, olefinsulfonates, methyl ester sulfonates,
sulfo fatty acids, alkyl sulfates, mono- and dialkyl
sulfosuccinates, mono- and dialkyl sulfosuccinamates,
sulfotriglycerides, amide soaps, ethercarboxylic acids and salts
thereof, fatty acid isethionates, fatty acid sarcosinates, fatty
acid taurides, N-acylamino acids, for example acyl lactylates, acyl
tartrates, acyl glutamates and acyl aspartates, alkyl
oligoglucoside sulfates, alkylglucose carboxylates, protein fatty
acid condensates and alkyl (ether) phosphates.
[0592] A first preferred embodiment is that of anionic surfactants
of the sulfonate and sulfate types. Preferred surfactants of the
sulfonate type are C.sub.9-C.sub.13-alkylbenzene sulfonates,
olefinsulfonates, i.e. mixtures of alkene- and
hydroxyalkanesulfonates, and disulfonates as obtained, for example,
from C.sub.12-C.sub.18-monoolefins having a terminal or internal
double bond by sulfonation with gaseous sulfur trioxide and
subsequent alkaline or acidic hydrolysis of the sulfonation
products. Also suitable are alkanesulfonates which are obtained
from C.sub.12-C.sub.18-alkanes, for example, by sulfochlorination
or sulfoxidation with subsequent hydrolysis and/or neutralization.
Also likewise suitable are the esters of .alpha.-sulfo fatty acids
(estersulfonates), for example the .alpha.-sulfonated methyl esters
of hydrogenated coconut, palm kernel or tallow fatty acids. Further
suitable anionic surfactants are sulfated fatty acid glycerol
esters. Fatty acid glycerol esters are understood to mean, inter
alia, the mono-, di- and triesters, and mixtures thereof, as
obtained in the preparation by esterification of a monoglycerol
with 1 to 3 mol of fatty acid or in the transesterification of
triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated
fatty acid glycerol esters here are the sulfation products of
saturated fatty acids having 6 to 22 carbon atoms, for example of
caproic acid, caprylic acid, capric acid, myristic acid, lauric
acid, palmitic acid, stearic acid or behenic acid.
[0593] Preferred alk(en)yl sulfates are the alkali metal and
especially the sodium salts of the sulfuric monoesters of
C.sub.12-C.sub.18-fatty alcohols, for example of coconut alcohol,
tallow alcohol or lauryl, myristyl, cetyl or stearyl alcohol, or of
the C.sub.10-C.sub.20-oxo process alcohols and the monoesters of
secondary C.sub.10-C.sub.20-alcohols. Additionally preferred are
alk(en)yl sulfates comprising a synthetic petrochemical-based
straight-chain C.sub.10-C.sub.20-alkyl radical. These have
analogous degradation behavior to the equivalent compounds based on
oleochemical raw materials. From the point of view of washing,
preference is given to the C.sub.12-C.sub.16-alkyl sulfates and
C.sub.12-C.sub.15-alkyl sulfates, and also C.sub.14-C.sub.15-alkyl
sulfates. 2,3-Alkyl sulfates, which are prepared, for example,
according to U.S. Pat. No. 3,234,258 or 5,075,041 and can be
obtained as commercial products from Shell Oil Company under the
DAN.RTM. name, are also suitable anionic surfactants. Also suitable
among other substances are the sulfuric monoesters of the
straight-chain or branched C.sub.7-C.sub.21 alcohols which have
been ethoxylated with 1 to 6 mol of ethylene oxide, such as
2-methyl-branched C.sub.9-C.sub.11 alcohols with an average of 3.5
mol of ethylene oxide (EO) or C.sub.12-C.sub.18 fatty alcohols with
1 to 4 EO. Owing to their high foaming level, they are
conventionally used in cleaning compositions only in relatively
small amounts, for example in amounts of 1% to 5% by weight.
Further suitable anionic surfactants in the context of the present
invention are also the salts of alkylsulfosuccinic acid, which are
also referred to as sulfosuccinates or as sulfosuccinic acid esters
and are the monoesters and/or diesters of sulfosuccinic acid with
alcohols, preferably fatty alcohols and especially ethoxylated
fatty alcohols. Preferred sulfosuccinates comprise C.sub.8-C.sub.18
fatty alcohol radicals or mixtures of these. Particularly preferred
sulfosuccinates comprise a fatty alcohol radical derived from
ethoxylated fatty alcohols. Particular preference is given here in
turn to sulfosuccinates wherein the fatty alcohol radicals are
derived from ethoxylated fatty alcohols having a narrow homolog
distribution. It is likewise also possible to use alk(en)ylsuccinic
acid having preferably 8 to 18 carbon atoms in the alk(en)yl chain
or salts thereof.
[0594] Particularly preferred anionic surfactants are soaps.
Saturated and unsaturated fatty acid soaps are suitable, such as
the salts of lauric acid, myristic acid, palmitic acid, stearic
acid, (hydrogenated) erucic acid and behenic acid, and especially
soap mixtures derived from natural fatty acids, for example coconut
fatty acids, palm kernel fatty acids, olive oil fatty acids or
tallow fatty acids.
[0595] The anionic surfactants including the soaps may be present
in the form of their sodium, potassium or ammonium salts, or as
soluble salts of organic bases, such as mono-, di- or
triethanolamine. The anionic surfactants are preferably in the form
of their sodium or potassium salts, especially in the form of the
sodium salts.
[0596] Suitable surfactants B) are also cationic surfactants.
Particularly preferred cationic surfactants are: [0597]
C.sub.7-C.sub.25-alkylamines; [0598] N,
N-dimethyl-N-(hydroxy-C.sub.7-C.sub.25-alkyl)ammonium salts; [0599]
mono- and diC.sub.7-C.sub.25-alkyl)dimethylammonium compounds
quaternized with alkylating agents; [0600] ester quats, especially
quaternary esterified mono-, di- and trialkanolamines esterified
with C.sub.8-C.sub.22-carboxylic acids; [0601] imidazoline quats,
especially 1-alkylimidazolinium salts of the formulae VII or
VIII
##STR00006##
[0602] where the variables are defined as follows: [0603] R.sup.18
is C.sub.1-C.sub.25-alkyl or C.sub.2-C.sub.25-alkenyl, [0604]
R.sup.19 is C.sub.1-C.sub.4-alkyl or hydroxy-C.sub.1-C.sub.4-alkyl,
[0605] R.sup.20 is C.sub.1-C.sub.4-alkyl,
hydroxy-C.sub.1-C.sub.4-alkyl or an
R.sup.21--(CO)--R.sup.22--(CH.sub.2).sub.r radical where R.sup.21
is H or C.sub.1-C.sub.4-alkyl, R.sup.22 is --O-- or --NH-- and r is
2 or 3,
[0606] where at least one R.sup.18 radical is a
C.sub.7-C.sub.22-alkyl radical.
[0607] The surfactants B) may also be amphoteric surfactants.
Suitable amphoteric surfactants are alkyl betaines, alkyl
amidobetaines, alkyl sulfobetaines, aminopropionates,
aminoglycinates and amphoteric imidazolium compounds. For example,
it is possible to use cocodimethylsulfopropyl betaine, lauryl
betaine, cocamidopropyl betaine, sodium cocamphopropionate or
tetradecyldimethylamine oxide.
[0608] The content of surfactants in washing and cleaning
compositions in liquid and gel form is preferably 2% to 75% by
weight and especially 5% to 65% by weight, based in each case on
the overall composition.
[0609] The content of surfactants in solid washing and cleaning
compositions is preferably 2% to 40% by weight and especially 5% to
35% by weight, based in each case on the overall composition.
[0610] Component C)
[0611] Builders, which are sometimes also referred to as
sequestrant, complexing agent, chelator, chelating agent or
softener, bind alkaline earth metals and other water-soluble metal
salts without precipitation. They help to break up soil, disperse
soil particles and help to detach soil, and sometimes themselves
have a washing effect.
[0612] Suitable builders may either be organic or inorganic in
nature. Examples are aluminosilicates, carbonates, phosphates and
polyphosphates, polycarboxylic acids, polycarboxylates,
hydroxycarboxylic acids, phosphonic acids, e.g.
hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic
acids and salts thereof and polymeric compounds containing
carboxylic acid groups, and salts thereof.
[0613] Suitable inorganic builders are, for example, crystalline or
amorphous aluminosilicates having ion-exchanging properties, such
as zeolites. Different types of zeolites are suitable, especially
zeolites A, X, B, P, MAP and HS in their sodium form or in forms in
which sodium has been partly exchanged for other cations such as
Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for
example, in U.S. Pat. No. 4,604,224. Crystalline silicates suitable
as builders are, for example, disilicates or sheet silicates, e.g.
5-Na.sub.2Si.sub.2O.sub.5 or B--Na.sub.2Si.sub.2O.sub.5(SKS 6 or
SKS 7). The silicates can be used in the form of their alkali
metal, alkaline earth metal or ammonium salts, preferably as
sodium, lithium and magnesium silicates. Likewise usable are
amorphous silicates, for example sodium metasilicate having a
polymeric structure, or amorphous disilicate (Britesil.RTM. H 20,
manufacturer: Akzo). Among these, preference is given to sodium
disilicate.
[0614] Suitable inorganic builder substances based on carbonate are
carbonates and hydrogencarbonates. These can be used in the form of
their alkali metal, alkaline earth metal or ammonium salts.
Preference is given to using sodium carbonates and
hydrogencarbonates, lithium carbonates and hydrogencarbonates and
magnesium carbonates and hydrogencarbonates, especially sodium
carbonate and/or sodium hydrogencarbonate.
[0615] Customary phosphates used as inorganic builders are alkali
metal orthophosphates and/or polyphosphates, for example
pentasodium triphosphate.
[0616] Suitable organic builders are, for example,
C.sub.4-C.sub.30-di-, -tri- and -tetracarboxylic acids, for example
succinic acid, propanetricarboxylic acid, butanetetracarboxylic
acid, cyclopentanetetracarboxylic acid and alkyl- and
alkenylsuccinic acids having C.sub.2-C.sub.20-alkyl or -alkenyl
radicals.
[0617] Suitable organic builders are also hydroxycarboxylic acids
and polyhydroxycarboxylic acids (sugar acids). These include
C.sub.4-C.sub.20-hydroxycarboxylic acids, for example malic acid,
tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric
acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic
acid, and sucrosemono-, -di- and -tricarboxylic acid. Among these,
preference is given to citric acid and salts thereof.
[0618] Suitable organic builders are additionally phosphonic acids,
for example hydroxy alkylphosphonic acids, aminophosphonic acids
and the salts thereof. These include, for example,
phosphonobutanetricarboxylic acid, aminotrismethylenephosphonic
acid, ethylenediaminetetraethylenephosphonic acid,
hexamethylenediaminetetramethylene phosphonic acid,
diethylenetriaminepentamethylenephosphonic acid, morpholino
methanediphosphonic acid, 1-hydroxy-C.sub.1- to
-C.sub.10-alkyl-1,1-diphosphonic acids such as
1-hydroxyethane-1,1-diphosphonic acid. Among these, preference is
given to 1-hydroxyethane-1,1-diphosphonic acid and salts
thereof.
[0619] Suitable organic builders are also aminopolycarboxylic
acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic
dipropionic acid, nitrilotripropionic acid, .beta.-alaninediacetic
acid (.beta.-ADA), ethylenediaminetetraacetic acid (EDTA),
diethylenetriaminepentaacetic acid,
propylene-1,3-diaminetetraacetic acid,
propylene-1,2-diaminetetraacetic acid,
N-(alkyl)ethylenediaminetriacetic acid,
N-(hydroxyalkyl)-ethylenediaminetriacetic acid,
ethylenediaminetriacetic acid, cyclohexylene-1,2-diaminetetraacetic
acid, iminodisuccinic acid, hydroxyiminodisuccinic acid,
ethylenediaminedisuccinic acid, serinediacetic acid,
isoserinediacetic acid, L-asparaginediacetic acid, L-glutamine
diacetic acid, glutamic acid, diacetic acid, methylglycinediacetic
acid (MGDA) and the salts of the aforementioned aminopolycarboxylic
acids. Preference is given to methylglycinediacetic acid, glutamic
acid diacetic acid and salts thereof. The salts of
methylglycinediacetic acid may be in racemic form, meaning that D
and L enantiomers are present in an equimolar mixture, or one
enantiomer, e.g. the L enantiomer, may be present in excess.
[0620] Suitable organic builders are also polymeric compounds
containing carboxylic acid groups, such as acrylic acid
homopolymers. These preferably have a number-average molecular
weight in the range from 800 to 70 000 g/mol, more preferably from
900 to 50 000 g/mol, particularly 1000 to 20 000 g/mol and
especially 1000 to 10 000 g/mol. In this context, the term "acrylic
acid homopolymer" also encompasses polymers in which the carboxylic
acid groups are in partly or fully neutralized form. These include
acrylic acid homopolymers in which the carboxylic acid groups are
present partly or completely in the form of alkali metal salts or
ammonium salts. Preference is given to acrylic acid homopolymers in
which the carboxylic acid groups are protonated or are partly or
completely in the form of sodium salts.
[0621] Suitable polymeric compounds containing carboxylic acid
groups are also oligomaleic acids, as described, for example, in
EP-A 451 508 and EP-A 396 303.
[0622] Suitable polymeric compounds containing carboxylic acid
groups are also terpolymers of unsaturated C.sub.4-C.sub.8
dicarboxylic acids, which may include copolymerized
monoethylenically unsaturated monomers from the group (i) mentioned
below in amounts of up to 95% by weight, from the group (ii) in
amounts of up to 60% by weight and from the group (iii) in amounts
of up to 20% by weight as comonomers. Suitable unsaturated
C.sub.4-C.sub.8 dicarboxylic acids here are, for example, maleic
acid, fumaric acid, itaconic acid and citraconic acid. Preference
is given to maleic acid. Group (i) encompasses monoethylenically
unsaturated C.sub.3-C.sub.8 monocarboxylic acids, for example
acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid.
From group (i), preference is given to using acrylic acid and
methacrylic acid. Group (ii) encompasses monoethylenically
unsaturated C.sub.2-C.sub.22 olefins, vinyl alkyl ethers having
C.sub.1-C.sub.8-alkyl groups, styrene, vinyl esters of
C.sub.1-C.sub.8 carboxylic acids, (meth)acrylamide and
vinylpyrrolidone. From group (ii), preference is given to using
C.sub.2-C.sub.6 olefins, vinyl alkyl ethers having
C.sub.1-C.sub.4-alkyl groups, vinyl acetate and vinyl propionate.
If the polymers of group (ii) comprise copolymerized vinyl esters,
these may also be in partly or fully hydrolyzed form to give vinyl
alcohol structural units. Suitable co- and terpolymers are known,
for example, from U.S. Pat. No. 3,887,806 and DE-A 4313909. Group
(iii) encompasses (meth)acrylic esters of C.sub.1-C.sub.8 alcohols,
(meth)acrylonitrile, (meth)acrylamides of C.sub.1-C.sub.8 amines,
N-vinylformamide and N-vinylimidazole.
[0623] Suitable polymeric compounds containing carboxylic acid
groups are also homopolymers of the monoethylenically unsaturated
C.sub.3-C.sub.8 monocarboxylic acids, for example acrylic acid,
methacrylic acid, crotonic acid and vinylacetic acid, especially of
acrylic acid and methacrylic acid, copolymers of dicarboxylic
acids, for example copolymers of maleic acid or itaconic acid and
acrylic acid in a weight ratio of 10:90 to 95:5, more preferably
those in a weight ratio of 30:70 to 90:10 with molar masses of 1000
to 150 000 g/mol; terpolymers of maleic acid, acrylic acid and a
vinyl ester of a C.sub.1-C.sub.3 carboxylic acid in a weight ratio
of 10 (maleic acid):90 (acrylic acid+vinyl ester) to 95 (maleic
acid):10 (acrylic acid+vinyl ester), where the weight ratio of
acrylic acid to the vinyl ester may vary within the range from
30:70 to 70:30; copolymers of maleic acid with C.sub.2-C.sub.8
olefins in a molar ratio of 40:60 to 80:20, particular preference
being given to copolymers of maleic acid with ethylene, propylene
or isobutene in a molar ratio of 50:50.
[0624] Suitable polymeric compounds containing carboxylic acid
groups are also copolymers of 50% to 98% by weight of ethylenically
unsaturated weak carboxylic acids with 2% to 50% by weight of
ethylenically unsaturated sulfonic acids, as described, for
example, in EP-A-0877002. Suitable weak ethylenically unsaturated
carboxylic acids are especially C.sub.3-C.sub.6 monocarboxylic
acids, such as acrylic acid and methacrylic acid. Suitable
ethylenically unsaturated sulfonic acids are
2-acetylamidomethyl-1-propanesulfonic acid,
2-methacrylamido-2-methyl-1-propanesulfonic acid,
2-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic
acid, methallylsulfonic acid, allyloxybenzenesulfonic acid,
methallyloxybenzenesulfonic acid,
2-hydroxy-3-(2-propenyloxy)propanesulfonic acid,
2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid,
vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl
methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and
salts of these acids. The copolymers may also comprise 0% to 30% by
weight of copolymerized ethylenically unsaturated C.sub.4-C.sub.8
dicarboxylic acids, such as maleic acid, and 0% to 30% by weight of
at least one monomer copolymerizable with the aforementioned
monomers. The latter monomer comprises, for example,
C.sub.1-C.sub.4-alkyl esters of (meth)acrylic acid,
C.sub.1-C.sub.4-hydroxyalkyl esters of (meth)acrylic acid,
acrylamide, alkyl-substituted acrylamide, N,N-dialkyl-substituted
acrylamide, vinylphosphonic acid, vinyl acetate, allyl alcohols,
sulfonated allyl alcohols, styrene and other vinylaromatics,
acrylonitrile, N-vinylpyrrolidone, N-vinyl formamide,
N-vinylimidazole or N-vinylpyridine. The weight-average molecular
weight of these copolymers is in the range from 3000 to 50 000
daltons. Copolymers with about 77% by weight of at least one
ethylenically unsaturated C.sub.3-C.sub.6 monocarboxylic acid and
about 23% by weight of at least one ethylenically unsaturated
sulfonic acid are particularly suitable.
[0625] Graft polymers of unsaturated carboxylic acids onto low
molecular weight carbohydrates or hydrogenated carbohydrates, cf.
U.S. Pat. No. 5,227,446, DE-A 4415623 and DE-A 4313909, are
likewise suitable. Suitable unsaturated carboxylic acids here are,
for example, maleic acid, fumaric acid, itaconic acid, citraconic
acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic
acid, and mixtures of acrylic acid and maleic acid, which are
grafted on in amounts of 40% to 95% by weight, based on the
component to be grafted. For the modification, it is additionally
possible for up to 30% by weight, based on the component to be
grafted, of further monoethylenically unsaturated monomers to be
present in copolymerized form. Suitable modifying monomers are the
aforementioned monomers of groups (ii) and (iii). Suitable graft
bases are degraded polysaccharides, for example acidically or
enzymatically degraded starches, inulins or cellulose, protein
hydrolyzates and reduced (hydrogenated or reductively aminated)
degraded polysaccharides, for example mannitol, sorbitol,
aminosorbitol and N-alkylglucamine, and also polyalkylene glycols
having molar masses with up to M.sub.w=5000, for example
polyethylene glycols, ethylene oxide/propylene oxide or ethylene
oxide/butylene oxide or ethylene oxide/propylene oxide/butylene
oxide block copolymers and alkoxylated mono- or polyhydric
C.sub.1-C.sub.22 alcohols (cf. U.S. Pat. No. 5,756,456).
[0626] Likewise suitable are polyglyoxylic acids as described, for
example, in EP-B-001004, U.S. Pat. No. 5,399,286, DE-A-4106355 and
EP-A-656914. The end groups of the polyglyoxylic acids can have
different structures.
[0627] Also suitable are polyamidocarboxylic acids and modified
polyamidocarboxylic acids; these are known, for example, from
EP-A-454126, EP-B-511037, WO-A94/01486 and EP-A-581452.
[0628] It is also possible to use polyaspartic acids and the alkali
metal salts thereof or cocondensates of aspartic acid with other
amino acids, for example with glycine, glutamic acid or lysine,
C.sub.4-C.sub.25 mono- or dicarboxylic acids and/or
C.sub.4-C.sub.25 mono- or diamines as polymeric compounds
containing carboxylic acid groups.
[0629] Among the polymeric compounds containing carboxylic acid
groups, preference is given to polyacrylic acids, also in partly or
fully neutralized form.
[0630] Suitable organic builders are also iminodisuccinic acid,
oxydisuccinic acid, amino polycarboxylates,
alkylpolyaminocarboxylates, aminopolyalkylenephosphonates,
polyglutamates, hydrophobically modified citric acid, for example
agaric acid, poly-[alpha]-hydroxyacrylic acid,
N-acylethylenediamine triacetates such as lauroylethylene diamine
triacetate, and alkylamides of ethylenediaminetetraacetic acid such
as EDTA tallow amide.
[0631] In addition, it is also possible to use oxidized starches as
organic builders.
[0632] Component D)
[0633] The bleach systems D) comprise at least one bleach and
optionally at least one further component selected from bleach
activators, bleach catalysts and bleach stabilizers.
[0634] Suitable bleaches are, for example, percarboxylic acids,
e.g. diperoxododecanedicarboxylic acid, phthalimidopercaproic acid
or monoperoxophthalic acid or -terephthalic acid, salts of
percarboxylic acids, e.g. sodium percarbonate, adducts of hydrogen
peroxide onto inorganic salts, e.g. sodium perborate monohydrate,
sodium perborate tetrahydrate, sodium carbonate perhydrate or
sodium phosphate perhydrate, adducts of hydrogen peroxide onto
organic compounds, e.g. urea perhydrate, or of inorganic peroxo
salts, e.g. alkali metal persulfates, or peroxodisulfates.
[0635] Suitable bleach activators are, for example, polyacylated
sugars, e.g. pentaacetylglucose; acyloxybenzenesulfonic acids and
their alkali metal and alkaline earth metal salts, e.g. sodium
p-nonanoyloxybenzenesulfonate or sodium
p-benzoyloxybenzenesulfonate; --N,N-diacylated and
N,N,N',N'-tetraacylated amines, e.g.
N,N,N',N'-tetraacetylmethylenediamine and -ethylenediamine (TAED),
N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylated
hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
N-alkyl-N-sulfonylcarboxamides, e.g. N-methyl-N-mesylacetamide or
N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides, acylated
triazoles or urazoles, e.g. monoacetylmaleic hydrazide;
O,N,N-trisubstituted hydroxylamines, e.g.
O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinyl
hydroxylamine or O,N,N-triacetylhydroxylamine;
N,N'-diacylsulfurylamides, e.g.
N,N'-dimethyl-N,N'-diacetylsulfurylamide or
N,N'-diethyl-N,N'-dipropionylsulfurylamide; acylated lactams, for
example acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam
or carbonylbiscaprolactam; anthranil derivatives, for example
2-methylanthranil or 2-phenylanthranil; triacyl cyanurates, e.g.
triacetyl cyanurate or tribenzoyl cyanurate; oxime esters and
bisoxime esters, for example O-acetylacetone oxime or
bisisopropyliminocarbonate; carboxylic anhydrides, e.g. acetic
anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic
anhydride; enol esters, for example isopropenyl acetate;
1,3-diacyl-4,5-diacyloxyimidazolines, e.g.
1,3-diacetyl-4,5-diacetoxyimidazoline; tetraacetylglycoluril and
tetrapropionylglycoluril; diacylated 2,5-diketopiperazines, e.g.
1,4-diacetyl-2,5-diketopiperazine; ammonium-substituted nitriles,
for example N-methylmorpholinioacetonitrile methylsulfate;
acylation products of propylenediurea and
2,2-dimethylpropylenediurea, e.g. tetraacetylpropylenediurea;
.alpha.-acyloxypolyacylmalonamides, e.g.
.alpha.-acetoxy-N,N'-diacetylmalonamide;
diacyldioxohexahydro-1,3,5-triazines, e.g.
1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
benz-(4H)-1,3-oxazin-4-ones with alkyl radicals, e.g. methyl, or
aromatic radicals e.g. phenyl, in the 2 position.
[0636] A bleach system composed of bleaches and bleach activators
may optionally also comprise bleach catalysts. Suitable bleach
catalysts are, for example, quaternized imines and sulfonimines,
which are described, for example, in U.S. Pat. No. 5,360,569 and
EP-A 453 003. Particularly effective bleach catalysts are manganese
complexes, which are described, for example, in WO-A 94/21777. In
the case of use thereof in the washing and cleaning compositions,
such compounds are incorporated in maximum amounts of up to 1.5% by
weight, especially up to 0.5% by weight, and in the case of very
active manganese complexes in amounts of up to 0.1% by weight. As
well as the bleach system composed of bleaches, bleach activators
and optionally bleach catalysts described, the use of systems with
enzymatic peroxide release or of photoactivated bleach systems is
also possible for the washing and cleaning compositions of the
invention.
[0637] Component E)
[0638] Suitable enzymes (=component E1) are those as customarily
used as industrial enzymes. These include both enzymes with optimal
activity in the neutral to alkaline pH range and enzymes with
optimal activity in the acidic pH range. In a specific embodiment,
component E1) additionally comprises at least one enzyme
stabilizer. Suitable enzyme stabilizers E1) are those as
customarily used.
[0639] The enzymes are preferably selected from aminopeptidases,
amylases, arabinases, carbohydrases, carboxypeptidases, catalases,
cellulases, chitinases, cutinases, cyclodextrin
glycosyltransferases, deoxyribonucleases, esterases, galactanases,
alpha-galactosidases, beta-galactosidases, glucanases,
glucoamylases, alpha-glucosidases, beta-glucosidases,
haloperoxidases, hydrolase invertases, isomerases, keratinases,
laccases, lipases, mannanases, mannosidases, oxidases, pectinolytic
enzymes, peptidoglutaminases, peroxidases, peroxygenases, phytases,
polyphenol oxidases, proteolytic enzymes, ribonucleases,
transglutaminases, transferases, xylanases and mixtures
thereof.
[0640] The enzymes are specifically selected from hydrolases, such
as proteases, esterases, glucosidases, lipases, amylases,
cellulases, mannanases, other glycosyl hydrolases and mixtures of
the aforementioned enzymes. All these hydrolases contribute to soil
dissolution and removal of protein-, grease- or starch-containing
soiling. Oxireductases can also be used for bleaching. Of
particularly good suitability are enzymatic active ingredients
obtained from bacterial strains or fungi such as Bacillus subtilis,
Bacillus licheniformis, Streptomyceus griseus and Humicola
insolens.
[0641] Preferred enzymes are described more particularly below:
[0642] Proteases:
[0643] Suitable proteolytic enzymes (proteases) may in principle be
of animal, vegetable or microbial origin. Preference is given to
proteolytic enzymes of microbial origin. These also include
chemically or genetically modified mutants.
[0644] Lipases:
[0645] Suitable lipases may in principle originate from bacteria or
fungi. These also include chemically or genetically modified
mutants.
[0646] Amylases:
[0647] In principle, all .alpha.- and/or .beta.-amylases are
suitable. Suitable amylases may in principle originate from
bacteria or fungi. These also include chemically or genetically
modified mutants.
[0648] Cellulases:
[0649] In principle, all cellulases are suitable. Suitable
cellulases may in principle originate from bacteria or fungi. These
also include chemically or genetically modified mutants.
[0650] Peroxidases/oxidases:
[0651] Suitable peroxidases/oxidases may in principle originate
from plants, bacteria or fungi. These also include chemically or
genetically modified mutants.
[0652] Lyases:
[0653] In principle, all lyases are suitable. Suitable lyases may
in principle originate from bacteria or fungi. These also include
chemically or genetically modified mutants.
[0654] Compositions of the invention may comprise further enzymes
which are referred to collectively by the term hemicellulases.
These include, for example, mannanases, xanthan lyases,
pectinylases (=pectinases), pectin esterases, xyloglucanases
(=xylanases), pullulanases and .beta.-glucanases.
[0655] Preferably, the washing or cleaning composition of the
invention comprises at least one enzyme selected from proteases,
amylases, mannanases, cellulases, lipases, pectin lyases and
mixtures thereof.
[0656] Preferably, the washing or cleaning composition of the
invention comprises at least one protease and/or amylase.
[0657] Preferably, the washing, cleaning or dishwashing composition
of the invention comprises an enzyme mixture. For example,
preference is given to enzyme mixtures comprising or consisting of
the following enzymes: [0658] protease and amylase, [0659] protease
and lipase (or lipolytic enzymes), [0660] protease and cellulase,
[0661] amylase, cellulase and lipase (or lipolytic enzymes), [0662]
protease, amylase and lipase (or lipolytic enzymes), [0663]
protease, lipase (or lipolytic enzymes) and cellulase.
[0664] The enzymes can be adsorbed onto carrier substances in order
to protect them from premature decomposition.
[0665] The washing or cleaning composition of the invention may
optionally also comprise enzyme stabilizers E1). These include, for
example, calcium propionate, sodium formate, boric acids, boronic
acids and salts thereof, such as 4-formylphenylboronic acid,
peptides and peptide derivatives, for example peptide aldehydes,
polyols, such as propane-1,2-diol, and mixtures thereof.
[0666] The washing or cleaning compositions of the invention
comprise the enzymes preferably in an amount of 0.1% to 5% by
weight, more preferably 0.12% to 2.5% by weight, based on the total
weight of the washing or cleaning compositions.
[0667] In order to impart the desired viscosity to liquid and
specifically aqueous compositions, it is additionally possible to
use at least one thickener (=component E2) as component E).
[0668] Suitable thickeners in principle are any known thickeners
(rheology modifiers), provided they do not have any adverse effect
on the action of the washing and cleaning composition. Suitable
thickeners may either be of natural origin or synthetic in
nature.
[0669] Examples of thickeners of natural origin are xanthan, carob
seed flour, guar flour, carrageenan, agar, tragacanth, gum arabic,
alginates, modified starches, such as hydroxyethyl starch, starch
phosphate esters or starch acetates, dextrins, pectins and
cellulose derivatives, such as carboxymethyl cellulose,
hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl
methyl cellulose, methyl cellulose and the like.
[0670] Thickeners of natural origin are also inorganic thickeners,
such as polysilicic acids and clay minerals, e.g. sheet silicates,
and also the silicates specified under the builders.
[0671] Examples of synthetic thickeners are polyacrylic and
polymethacrylic compounds, such as (partly) crosslinked
homopolymers of acrylic acid, for example homopolymers, crosslinked
with an allyl ether of sucrose or pentaerythritol or with
propylene, of acrylic acid (carbomer), e.g. the Carbopol.RTM.
brands from BF Goodridge (e.g. Carbopol.RTM. 676, 940, 941, 934 or
the like) or the Polygel.RTM. brands from 3V Sigma (e.g.
Polygel.RTM. DA), copolymers of ethylenically unsaturated mono- or
dicarboxylic acids, for example terpolymers of acrylic acid,
methacrylic acid or maleic acid with methyl or ethyl acrylate and a
(meth)acrylate derived from long-chain ethoxylated alcohols, for
example the Acusol.RTM. brands from Rohm & Haas (e.g.
Acusol.RTM. 820 or 1206A), copolymers of two or more monomers
selected from acrylic acid, methacrylic acid and their
C.sub.1-C.sub.4-alkyl esters, e.g. copolymers of methacrylic acid,
butyl acrylate and methyl methacrylate or of butyl acrylate and
methyl methacrylate, e.g. the Aculyn.RTM. and Acusol.RTM. brands
from Rohm & Haas (e.g. Aculyn.RTM. 22, 28 or 33 and Acusol.RTM.
810, 823 and 830), or crosslinked high molecular weight acrylic
acid copolymers, for example copolymers, crosslinked with an allyl
ether of sucrose or pentaerythritol, of C.sub.10-C.sub.30-alkyl
acrylates with one or more comonomers selected from acrylic acid,
methacrylic acid and their C.sub.1-C.sub.4-alkyl esters (e.g.
Carbopol.RTM. ETD 2623, Carbopol.RTM. 1382 or Carbopol.RTM. AQUA 30
from Rohm & Haas).
[0672] Examples of synthetic thickeners are also reaction products
of maleic acid polymers with ethoxylated long-chain alcohols, e.g.
the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119
from ISP; polyethylene glycols, polyamides, polyimines and
polycarboxylic acids.
[0673] Also suitable are mixtures of the aforementioned
thickeners.
[0674] Preferred thickeners are xanthans and the aforementioned
polyacrylic and polymethacrylic compounds.
[0675] Suitable organic solvents (=component E3) are selected from
mono- or polyhydric alcohols, alkanolamines or glycol ethers.
Preferably, they are selected from ethanol, n- or isopropanol,
butanols, glycol, propane- or butanediol, glycerol, diglycol,
propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl
ether, ethylene glycol ethyl ether, ethylene glycol propyl ether,
ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether,
diethylene glycol ethyl ether, propylene glycol methyl, ethyl or
propyl ether, dipropylene glycol monomethyl or -ethyl ether,
diisopropylene glycol monomethyl or -ethyl ether, methoxy, ethoxy
or butoxy triglycol, isobutoxyethoxy-2-propanol,
3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, and
mixtures of these solvents.
[0676] Useful foam inhibitors or defoamers (=component E4) are, for
example, soaps, paraffins or silicone oils, which can optionally be
applied to carrier materials.
[0677] Suitable bases (=component E5) are alkali metal hydroxides,
alkaline earth metal hydroxides, alkali metal carbonates, alkaline
earth metal carbonates, ammonium carbonate, alkali metal
hydrogencarbonates, alkaline earth metal hydrogencarbonates,
ammonium hydrogencarbonates and mixtures thereof. Preference is
given to using sodium, lithium and magnesium carbonates or sodium,
lithium and magnesium hydrogencarbonates, especially sodium
carbonate and/or sodium hydrogencarbonate.
[0678] In addition, the washing or cleaning compositions of the
invention may comprise further additives E6) which further improve
the performance and/or aesthetic properties. In general, preferred
compositions comprise, in addition to the aforementioned
components, at least one further additive selected from
electrolytes, pH modifiers, perfume carriers, bitter substances,
fluorescers, hydrotropes, antiredeposition agents, optical
brighteners, graying inhibitors, antishrink agents, anticrease
agents, dye transfer inhibitors, antimicrobial active ingredients,
antioxidants, anti-yellowing agents, corrosion inhibitors,
antistats, ironing aids, hydrophobizing and impregnating agents,
antiswell and antislip agents, and UV absorbers.
[0679] Suitable dye transfer inhibitors are especially homo- or
copolymers comprising at least one copolymerized monomer selected
from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole,
2-vinylpyridine, 4-vinylpyridine, salts of the three latter
monomers, 4-vinylpyridine N-oxide,
N-carboxymethyl-4-vinylpyridinium halides and mixtures thereof.
[0680] Suitable graying inhibitors and/or washing power boosters
are especially: [0681] carboxymethylcellulose, [0682] graft
polymers of vinyl acetate onto carbohydrates, for example onto
degraded starch, [0683] graft polymers of vinyl acetate onto
polyethylene glycol, [0684] alkoxylated oligo- and polyamines, e.g.
ethoxylated hexamethylenediamine, which may additionally also be in
quaternized and/or sulfated form, or alkoxylated polyethyleneimine
with 16 to 24 EO per NH, [0685] copolymers based on styrene and
maleic acid which may additionally also have been modified with end
group-capped polyethylene glycol, [0686] copolymers based on
styrene and acrylic acid.
[0687] In order to improve the aesthetic impression of the washing,
cleaning or dishwashing compositions of the invention, they can be
colored with suitable dyes. Preferred dyes, the selection of which
does not present any difficulty at all to the person skilled in the
art, have high storage stability and insensitivity to the other
constituents of the compositions and to light, and also no marked
substantivity with respect to textile fibers, in order not to stain
them.
[0688] The washing, cleaning or dishwashing compositions of the
invention may comprise at least one bitter substance. Bitter
substances are specially used in order to prevent inadvertent
swallowing of the compositions, for example by infants. Suitable
bitter substances are known to those skilled in the art. These
include, for example, denatonium benzoate
(benzyldiethyl-(2,6-xylylcarbamoyl)methylammonium benzoate), the
bitterest-tasting substance known to date, which is commercially
available under the Bitrex.RTM. name.
[0689] Dishwashing Compositions
[0690] The above-described multilayer films of the invention are
also particularly advantageously suitable for at least partial
coating or ensheathing of dishwashing detergents, especially of
dishwashing detergents for machine dishwashing processes (automatic
dishwashing, ADW). The polymer composition P1) present in the
multilayer films exerts a dispersing, film-inhibiting, emulsifying
and/or surfactant effect in dishwashing detergents. In addition,
they ensure good rinse aid and/or drying performance. Examples of
formulations of the invention for dishwashing include machine
dishwashing compositions, rinse aids and machine dishwashing
detergents with rinse aid function.
[0691] Machine dishwashing processes in the domestic and commercial
sector comprise a plurality of successive steps, the first
comprising the mechanical removal of loosely adhering food residues
and the second the actual cleaning operation with the aid of a
machine dishwasher, and the third generally consisting of a rinsing
step, which is followed by the drying of the cleaned dishware.
These operations are conducted in more or less automated form, the
central unit used being a machine dishwasher in which at least the
cleaning step and generally also the subsequent rinsing step and/or
the drying step are conducted.
[0692] In machine dishwashers for the domestic sector, the soiled
dishware is generally cleaned in a single chamber, and the
aforementioned treatment steps proceed successively in a controlled
program. Fresh water passes through the softening unit to the pump
well and is sprayed by means of moving spray arms over the ware to
be rinsed. Water-insoluble substances rinsed off are filtered out
in the pump well. In the second rinse cycle, a generally alkaline
cleaning composition is added to the rinse water, heated to the set
temperature and distributed over the ware to be rinsed. In the last
rinse cycle, a rinse aid is added to the treatment liquid, which
reduces the surface tension, as a result of which the treatment
liquid runs more easily off the ware. After the last rinse cycle,
the contents are dried. The components used in the rinse cycle,
such as water treatment agents, cleaning compositions, rinse aids,
etc., can be used either in the form of individual components or in
multicomponent formulations. Multifunctional detergents of this
kind comprise surfactants for rinsing and a polymer for water
softening. In that case, it is unnecessary to separately dispense a
rinse aid and a salt for water softening into the machine
dishwasher.
[0693] Commercial machine dishwashers consist basically of
stationary bath tanks from which an essentially aqueous cleaning
solution is jetted or sprayed onto the dishware, which moves past
these baths on a conveyor belt, such that the used solution flows
back into the bath tanks again. Water enters the last bath tank,
flows via overflows in the manner of a cascade through all the
other tanks and leaves the machine via the overflow of the first
tank. The application of a generally highly alkaline cleaning
solution generally takes place with the aid of nozzles provided
therefor, or of a specific spraying system normally arranged in the
middle region of the machine.
[0694] The multilayer films of the invention are suitable for at
least partial coating or ensheathing of dishwashing compositions
for machine dishwashing, which especially feature excellent
film-inhibiting action. Preferred machine dishwashing composition
formulations have inhibiting action with respect to both inorganic
and organic film deposits. The inorganic film deposits are
especially calcium and magnesium phosphate, calcium and magnesium
carbonate, calcium and magnesium silicate and/or calcium and
magnesium phosphonate, which arise from the calcium and magnesium
salts present in the water and the builders present in standard
dishwashing compositions. The organic film deposits are especially
soil constituents from the rinse liquor, for example protein,
starch and fat deposits. The formulations used in accordance with
the invention for machine dishwashing are also effective against
carry-over deposits, which originate from the residual water in the
bottom of the machine dishwasher and comprise, inter alia,
dishwashing composition residues and possibly also soil residues
from the previous wash cycle of the machine dishwasher.
[0695] The dishwashing composition of the invention preferably
comprises the following constituents: [0696] Ga) at least one
sheath and/or coating comprising or consisting of a multilayer film
of the invention, [0697] Gb) optionally at least one complexing
agent, [0698] Gc) at least one builder and/or cobuilder, [0699] Gd)
at least one nonionic surfactant, [0700] Ge) optionally at least
one component selected from bleaches, bleach activators and bleach
catalysts, [0701] Gf) optionally at least one enzyme, [0702] Gg)
optionally at least one further additive, preferably selected from
anionic or zwitterionic surfactants, alkali carriers, polymeric
dispersants, corrosion inhibitors, defoamers and foam inhibitors,
dyes, fragrances, bitter substances, fillers, tablet disintegrants,
organic solvents, tableting aids, disintegrants, thickeners and
solubilizers, [0703] Gh) optionally water.
[0704] A preferred dishwashing composition of the invention
comprises: [0705] Ga) 0.1% to 30% by weight of at least one sheath
and/or coating comprising or consisting of a multilayer film of the
invention, [0706] Gb) 0% to 50% by weight of at least one
complexing agent, [0707] Gc) 0.1% to 80% by weight of at least one
builder and/or cobuilder, [0708] Gd) 0.1% to 20% by weight of at
least one nonionic surfactant, [0709] Ge) 0% to 30% by weight of at
least one component selected from bleaches, bleach activators and
bleach catalysts, [0710] Gf) 0% to 8% by weight of at least one
enzyme, [0711] Gg) 0% to 50% by weight of at least one further
additive, preferably selected from anionic or zwitterionic
surfactants, alkali carriers, polymeric dispersants, corrosion
inhibitors, defoamers and foam inhibitors, dyes, fragrances, bitter
substances, fillers, tablet disintegrants, organic solvents,
tableting aids, disintegrants, thickeners and solubilizers, and
[0712] Gh) 0% to 99.7% by weight of water,
[0713] with the proviso that the weights of the components add up
to 100% by weight.
[0714] With regard to suitable and preferred multilayer films Ga),
reference is made to the general details relating to suitable and
preferred multilayer films.
[0715] Complexing agents Gb) which may be used are, for example:
nitrilotriacetic acid, ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid,
hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic
acid, glutamic acid diacetic acid, iminodisuccinic acid,
hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid,
aspartic acid diacetic acid, and also salts thereof in each case.
Preferred complexing agents Gb) are methylglycinediacetic acid and
glutamic acid diacetic acid and salts thereof. Particularly
preferred complexing agents Gb) are methylglycinediacetic acid and
salts thereof, especially the mono-, di- and trisodium, -potassium,
-lithium and -ammonium salts. The salts of methylglycinediacetic
acid may be in racemic form, meaning that D and L enantiomers are
present in an equimolar mixture, or one enantiomer, e.g. the L
enantiomer, may be present in excess. Preference is given in
accordance with the invention to 3% to 50% by weight of complexing
agent Gb).
[0716] Builders and/or co-builders Gc) used may especially be
water-soluble or water-insoluble substances having the main task of
binding calcium and magnesium ions. These may be low molecular
weight carboxylic acids and also salts thereof such as alkali metal
citrates, in particular anhydrous trisodium citrate or trisodium
citrate dihydrate, alkali metal succinates, alkali metal malonates,
fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl
disuccinates, gluconic acids, oxadiacetates,
carboxymethyloxysuccinates, tartrate monosuccinate, tartrate
disuccinate, tartrate monoacetate, tartrate diacetate and
.alpha.-hydroxypropionic acid.
[0717] A further substance class with cobuilder properties which
may be present in the dishwashing compositions of the invention is
that of the phosphonates. These are in particular
hydroxyalkanephosphonates or aminoalkanephosphonates. Among the
hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP)
is of particular significance as cobuilder. It is preferably used
in the form of the sodium salt, the disodium salt giving a neutral
reaction and the tetrasodium salt an alkaline reaction (pH 9).
Suitable aminoalkanephosphonates are preferably
ethylenediaminetetramethylenephosphonate (EDTMP),
diethylenetriaminepentamethylenephosphonate (DTPMP) and the higher
homologs thereof. They are preferably used in the form of the
neutral sodium salts, for example as the hexasodium salt of EDTMP
or as heptasodium and octasodium salts of DTPMP. The builder used
in this case is from the class of the phosphonates, preferably
HEDP. Aminoalkanephosphonates additionally have a pronounced heavy
metal binding capacity. Accordingly, it may be preferable to use
aminoalkanephosphonates, particularly DTPMP, or mixtures of the
phosphonates mentioned, particularly if the compositions also
comprise bleach.
[0718] Silicates may be used, inter alia, as builders. Crystalline
sheet silicates having the general formula NaMSi.sub.xO.sub.2x+1
yH.sub.2O may be present, where M is sodium or hydrogen, x is a
number from 1.9 to 22, preferably from 1.9 to 4, particularly
preferred values for x being 2, 3 or 4, and y is a number from 0 to
33, preferably 0 to 20. In addition, amorphous sodium silicates
having an SiO.sub.2:Na.sub.2O ratio of 1 to 3.5, preferably 1.6 to
3 and in particular 2 to 2.8 may be used.
[0719] Furthermore, in the context of the dishwashing composition
of the invention, builders and/or co-builders Gc) used may be
carbonates and hydrogen carbonates, among which the alkali metal
salts, particularly sodium salts, are preferred.
[0720] Furthermore, the cobuilders used may be homopolymers and
copolymers of acrylic acid or methacrylic acid preferably having a
weight-average molar mass of 2000 to 50 000 g/mol. Suitable
comonomers are in particular monoethylenically unsaturated
dicarboxylic acids such as maleic acid, fumaric acid and itaconic
acid and also anhydrides thereof such as maleic anhydride. Also
suitable are comonomers containing sulfonic acid groups such as
2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and
methanesulfonic acid. Hydrophobic comonomers are also suitable, for
example isobutene, diisobutene, styrene, alpha-olefins with 10 or
more carbon atoms. Hydrophilic monomers having hydroxyl functions
or alkylene oxide groups may also be used as comonomers. Examples
include: allyl alcohol and isoprenol and also alkoxylates thereof
and methoxypolyethylene glycol (meth)acrylate.
[0721] The dishwashing compositions of the invention preferably
comprise builders and/or cobuilders Gc) in an amount of 5% to 80%
by weight, more preferably 10% to 75% by weight, especially 15% to
70% by weight, more especially 15% to 65% by weight, based on the
total weight of the dishwashing composition.
[0722] Suitable nonionic surfactants Gd) are, for example, weakly
foaming or low-foaming nonionic surfactants. The dishwashing
compositions of the invention comprise nonionic surfactants
preferably in an amount of 0.1% to 20% by weight, more preferably
of 0.1% to 15% by weight, especially of 0.25% to 10% by weight,
especially of 0.5% to 10% by weight, based on the total weight of
the dishwashing composition. Suitable nonionic surfactants include
surfactants of the general formula (IX)
R.sup.31--O--(CH.sub.2CH.sub.2O).sub.a--(CH
R.sup.32CH.sub.2O).sub.b--R.sup.33 (IX),
[0723] in which R.sup.31 is a linear or branched alkyl radical
having 8 to 22 carbon atoms, R.sup.32 and R.sup.33 are each
independently hydrogen or a linear or branched alkyl radical having
1 to 10 carbon atoms or H, where R.sup.32 is preferably methyl, and
a and b are each independently 0 to 300. Preferably, a=1 to 100 and
b=0 to 30.
[0724] Also suitable in the context of the present invention are
surfactants of formula (X)
R.sup.34--O--[CH.sub.2CH(CH.sub.3)O].sub.c[CH.sub.2CH.sub.2O].sub.d[CH.s-
ub.2CH(CH.sub.3)O].sub.eCH.sub.2CH(OH)R.sup.35 (X),
[0725] in which R.sup.34 is a linear or branched aliphatic
hydrocarbyl radical having 4 to 22 carbon atoms or mixtures
thereof,
[0726] R.sup.35 is a linear or branched hydrocarbyl radical having
2 to 26 carbon atoms or refers to mixtures thereof,
[0727] c and e have values between 0 and 40, and
[0728] d is a value of at least 15.
[0729] Also suitable in the context of the present invention are
surfactants of formula (XI)
R.sup.36O--(CH.sub.2CH
R.sup.37O).sub.f(CH.sub.2CH.sub.2O).sub.g(CH.sub.2CH
R.sup.38O).sub.h--CO--R.sup.39 (XI),
[0730] in which
[0731] R.sup.36 is a branched or unbranched alkyl radical having 8
to 16 carbon atoms,
[0732] R.sup.37, R.sup.38 are each independently H or a branched or
unbranched alkyl radical having 1 to 5 carbon atoms,
[0733] R.sup.39 is an unbranched alkyl radical having 5 to 17
carbon atoms,
[0734] f, h are each independently a number from 1 to 5, and
[0735] g is a number from 13 to 35.
[0736] The surfactants of the formulae (IX), (X) and (XI) may be
either random copolymers or block copolymers; they are preferably
block copolymers. Furthermore, in the context of the present
invention, di- and multi-block copolymers constructed from ethylene
oxide and propylene oxide can be used, which are commercially
available, for example, under the name Pluronic.RTM. (BASF SE) or
Tetronic.RTM. (BASF Corporation). Furthermore, reaction products of
sorbitan esters with ethylene oxide and/or propylene oxide can be
used. Amine oxides or alkyl glycosides are also suitable. An
overview of suitable nonionic surfactants are disclosed in EP-A 851
023 and DE-A 198 19 187. Mixtures of two or more different nonionic
surfactants may also be present. The dishwashing compositions of
the invention may further comprise anionic or zwitterionic
surfactants, preferably in a mixture with nonionic surfactants.
Suitable anionic and zwitterionic surfactants are likewise
specified in EP-A 851 023 and DE-A 198 19 187.
[0737] Bleaches and bleach activators Ge) used in connection with
the dishwashing compositions of the invention may be
representatives known to those skilled in the art. Bleaches are
subdivided into oxygen bleaches and chlorine bleaches. Oxygen
bleaches used are alkali metal perborates and hydrates thereof, and
also alkali metal percarbonates. Preferred bleaches in this context
are sodium perborate in the form of the mono- or tetrahydrate,
sodium percarbonate or the hydrates of sodium percarbonate.
Likewise useable as oxygen bleaches are persulfates and hydrogen
peroxide. Typical oxygen bleaches are also organic peracids such as
perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid,
peroxystearic acid, phthalimidoperoxycaproic acid,
1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid,
diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-dioic acid.
In addition, the following oxygen bleaches can also be used in the
dishwashing composition: cationic peroxy acids, which are described
in the patent applications U.S. Pat. Nos. 5,422,028, 5,294,362 and
5,292,447, and sulfonylperoxy acids, which are described in the
patent application U.S. Pat. No. 5,039,447. Oxygen bleaches can be
used in amounts of generally 0.1% to 30% by weight, preferably of
1% to 20% by weight, more preferably of 3% to 15% by weight, based
on the overall dishwashing composition.
[0738] Chlorine bleaches and the combination of chlorine bleaches
with peroxide bleaches can also be used in connection with the
dishwashing compositions of the invention. Known chlorine bleaches
are, for example, 1,3-dichloro-5,5-dimethylhydantoin,
N-chlorosulfamide, chloramine T, dichloramine T, chloramine B,
N,N'-dichlorobenzoyl urea, p-toluenesulfonedichloroamide or
trichloroethylamine. Preferred chlorine bleaches in this case are
sodium hypochlorite, calcium hypochlorite, potassium hypochlorite,
magnesium hypochlorite, potassium dichloroisocyanurate or sodium
dichloroisocyanurate. Chlorine bleaches in this connection can be
used in amounts of 0.1% to 30% by weight, preferably of 0.1% to 20%
by weight, preferably of 0.2% to 10% by weight, more preferably of
0.3% to 8% by weight, based on the overall dishwashing
composition.
[0739] In addition, small amounts of bleach stabilizers, for
example phosphonates, borates, metaborates, metasilicates or
magnesium salts, may be added.
[0740] Bleach activators in the context of the present invention
can be compounds which, under perhydrolysis conditions, give rise
to aliphatic peroxocarboxylic acids having preferably 1 to 10
carbon atoms, in particular 2 to 4 carbon atoms, and/or substituted
perbenzoic acid. In this case, suitable compounds comprise, inter
alia, one or more N or O-acyl groups and/or optionally substituted
benzoyl groups, for example substances from the class of the
anhydrides, esters, imides, acylated imidazoles or oximes. Examples
are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine
(TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine
(TAHD), N-acylimides such as N-nonanoylsuccinimide (NOSI), acylated
phenol sulfonates such as n-nonanoyl- or
isononanoyloxybenzenesulfonate (n- or iso-NOBS), pentaacetylglucose
(PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or
isatoic anhydride (ISA). Also suitable as bleach activators are
nitrile quats such as N-methylmorpholinium acetonitrile salts (MMA
salts) or trimethylammonium acetonitrile salts (TMAQ salts).
Preferred suitable bleach activators are from the group consisting
of polyacylated alkylenediamines, more preferably TAED,
N-acylimides, more preferably NOSI, acylated phenolsulfonates, more
preferably n- or iso-NOBS, MMA, and TMAQ. Bleach activators in
connection with the present invention can be used in amounts of
0.1% to 30% by weight, preferably of 0.1% to 10% by weight,
preferably of 1% to 9% by weight, more preferably of 1.5% to 8% by
weight, based on the overall dishwashing composition.
[0741] In addition to the conventional bleach activators or in
place of them, so-called bleach catalysts may also be incorporated
in rinse aid particles. These substances are bleach-enhancing
transition metal salts or transition metal complexes such as salen
complexes or carbonyl complexes of manganese, iron, cobalt,
ruthenium or molybdenum. Also usable as bleach catalysts are
complexes of manganese, iron, cobalt, ruthenium, molybdenum,
titanium, vanadium and copper with nitrogen-containing tripod
ligands and also amine complexes of cobalt, iron, copper and
ruthenium.
[0742] As component Gf), the dishwashing compositions of the
invention may comprise 0% to 8% by weight of enzymes. If the
dishwashing compositions comprise enzymes, they comprise them
preferably in amounts of 0.1% to 8% by weight. Enzymes may be added
to the dishwashing composition in order to increase the cleaning
performance or to ensure the same quality of cleaning performance
under milder conditions (e.g. at low temperatures). The enzymes can
be used in free form or a form chemically or physically immobilized
on a support or in encapsulated form. The enzymes used most
frequently in this context include lipases, amylases, cellulases
and proteases. In addition, it is also possible, for example, to
use esterases, pectinases, lactases and peroxidases. Preference is
given in accordance with the invention to using amylases and
proteases.
[0743] In connection with the dishwashing compositions of the
invention, additives Gg) used may be, for example, anionic or
zwitterionic surfactants, alkali carriers, polymeric dispersants,
corrosion inhibitors, defoamers, dyes, fragrances, fillers, tablet
disintegrants, organic solvents, tableting aids, disintegrants,
thickeners, solubilizers or water. The alkali carriers used may be,
for example, in addition to the ammonium or alkali metal carbonates
already mentioned as builder substances, ammonium or alkali metal
hydrogencarbonates and ammonium or alkali metal sesquicarbonates,
and also ammonium or alkali metal hydroxides, ammonium or alkali
metal silicates and ammonium or alkali metal metasilicates and also
mixtures of the aforementioned substances.
[0744] The corrosion inhibitors used may be, inter alia, silver
anticorrosives from the group of the triazoles, the benzotriazoles,
the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles
and the transition metal salts or complexes.
[0745] To prevent glass corrosion, which is noticeable as
cloudiness, iridescence, streaks and lines on the glasses,
preference is given to using glass corrosion inhibitors. Preferred
glass corrosion inhibitors are, for example, magnesium, zinc and
bismuth salts and complexes and polyethyleneimines.
[0746] Paraffin oils and silicone oils may optionally be used in
accordance with the invention as defoamers and to protect plastics
and metal surfaces. Defoamers are used preferably in proportions of
0.001% by weight to 5% by weight. In addition, dyes, for example
patent blue, preservatives, for example Kathon CG, perfumes and
other fragrances may be added to the cleaning formulation of the
invention.
[0747] An example of a suitable filler in connection with the
dishwashing compositions of the invention is sodium sulfate.
[0748] Further possible additives that should be mentioned in
connection with the present invention include amphoteric and
cationic polymers.
[0749] In order to improve the aesthetic impression of the washing,
cleaning or dishwashing compositions of the invention, they can be
colored using suitable dyes. Preferred dyes, the selection of which
presents no difficulty whatsoever to the person skilled in the art,
have a high storage stability and insensitivity with respect to the
other ingredients of the compositions and to light, and do not have
any marked substantivity toward textile fibers, in order not to
stain them.
[0750] I & I Cleaners
[0751] The multilayer films of the invention are also suitable for
at least partial coating or ensheathing for industrial and
institutional cleaners (I & I cleaners). Industrial and
institutional cleaners are typically washing compositions,
all-purpose cleaners, foam cleaners, CIP (cleaning in place)
cleaners for professional and generally automated cleaning
operations, for example in industrial laundries, dairies,
breweries, the food and drink industry, the pharmaceutical industry
or pharmaceutical formulation, or sanitary cleaners.
[0752] The cleaners may be strongly basic with a high electrolyte
content and, if required, comprise bleaches (such as hydrogen
peroxide, sodium hypochlorite) or disinfectants and defoamers (for
example in bottle cleaning). It is also possible for the standard
aforementioned enzymes to be present in the industrial and
institutional cleaners. There is a great variety in terms of the
types of cleaning for which the formulations of the invention are
suitable. Examples include cleaning baths (stationary or mobile),
spray cleaning, ultrasound cleaning, steam jet cleaning and
high-pressure cleaning, optionally in combination with mechanical
cleaning, for example by means of rotating brushes.
[0753] Said formulations for cleaning include those for industry,
transport, commerce and industry, and for the private sector.
Specific examples include: professional laundries, professional
cleaning businesses, ore processing industry, metal and
metalworking industry, automobile and automobile supply industry,
electrical industry, electronics industry, photographic industry
and businesses, leisure industry and businesses, construction
material industry, brewing industry and businesses; foods industry
(e.g. processing or production of meat, poultry, dairy and fish
products), animal nutrition industry, cosmetics industry,
pharmaceutical industry, agrochemical industry, gastronomy, the
health sector, workshops, and public transport. Examples of objects
to be cleaned are institutional laundry, hospital laundry, laundry
from laundry collection, buildings containing living spaces, office
spaces or commercial spaces of a wide variety of different kinds,
and sanitary spaces, warehouses, breweries, small businesses such
as bakeries, butcheries and supermarkets; hospitals, care homes,
homes for the elderly, administration buildings, factory buildings,
doctors' practices; and also motor vehicles (cars and trucks),
buses, road tanker vehicles (interior and exterior), rail tanker
wagons, passenger vehicles and goods vehicles, and aircraft and
ships; and also building facades, tiled or painted walls, wooden
floors (parquet, boards) with screed or textile or plastics
coverings, signaling and lighting installations, furniture,
railings, overhead signage, other signage, safety reflectors,
delineating markers, tanks, dishware, glass panes, roads and paths,
outside paving, road and railway tunnels.
[0754] Acidic Sanitary Cleaners
[0755] The multilayer films of the invention are also suitable for
at least partial coating or ensheathing of cleaners for the
sanitary sector comprising at least one organic acid. Acidic
sanitary cleaners are especially suitable for WC cleaning, for
cleaning of washbasins, shower cubicles, shower trays and swimming
baths, and sinks in the kitchen sector. They are effective, for
example, in the removal of limescale and urine scale deposits and
in the removal of bacteria which typically form on the limescale
and urine scale deposits. They ensure cleanliness and effectively
prevent malodors. It has now been found that, surprisingly, the
multilayer films of the invention have high compatibility with
acidic surfactant compositions and are particularly advantageously
suitable for use in acidic sanitary cleaners.
[0756] A preferred acidic sanitary cleaner preferably comprises the
following constituents: [0757] at least one sheath and/or coating
comprising or consisting of a multilayer film of the invention as
defined above, or obtainable by a process as defined above, [0758]
at least one organic acid, [0759] optionally water, [0760]
optionally at least one thickener, and [0761] optionally at least
one further additive.
[0762] The acidic sanitary cleaner may be in solid, liquid or gel
form. The acidic sanitary cleaner is preferably in the liquid form
or especially in gel form.
[0763] Suitable organic acids are formic acid, acetic acid, citric
acid or methanesulfonic acid. Particular preference is given to
acetic acid or citric acid. The cleaner of the invention comprises
the organic acid preferably in an amount of 1% to 40% by weight,
especially of 5% to 15% by weight, based on the total weight of the
cleaner.
[0764] The cleaner of the invention preferably comprises at least
one surfactant in an amount of 0.5% to 50% by weight, especially of
1% to 15% by weight, based on the total weight of the cleaner.
[0765] Suitable thickeners are those mentioned above as component
E) for the washing and cleaning compositions of the invention, to
which reference is made here in full.
[0766] Suitable additives are those mentioned above as component E)
for the washing and cleaning compositions of the invention, to
which reference is made here in full. These especially include
stabilizers, dyes and fragrances.
[0767] Cosmetic and Pharmaceutical Compositions
[0768] The multilayer films of the invention are also suitable for
at least partial coating or ensheathing of cosmetic and
pharmaceutical products.
[0769] The cosmetic and pharmaceutical products may be in solid,
liquid or gel form.
[0770] Specifically, the cosmetic and pharmaceutical products take
the form of an aqueous formulation.
[0771] The invention further provides a cosmetic or pharmaceutical
composition comprising [0772] a) at least one sheath and/or coating
comprising or consisting of a multilayer film of the invention as
defined above, or obtainable by a process as defined above, [0773]
b) at least one cosmetically or pharmaceutically acceptable active,
and [0774] c) optionally at least one cosmetically or
pharmaceutically acceptable auxiliary other than components a) and
b).
[0775] Preferably, component c) comprises at least one cosmetically
or pharmaceutically acceptable carrier.
[0776] Preferably, the carrier component c) is selected from [0777]
i) water, [0778] ii) water-miscible organic solvents, preferably
C.sub.2-C.sub.4-alkanols, especially ethanol, [0779] iii) oils,
fats, waxes, [0780] iv) esters, other than iii), of
C.sub.6-C.sub.30-monocarboxylic acids with mono-, di- or trihydric
alcohols, [0781] v) saturated acyclic and cyclic hydrocarbons,
[0782] vi) fatty acids, [0783] vii) fatty alcohols, [0784] viii)
propellant gases,
[0785] and mixtures thereof.
[0786] Suitable hydrophilic components c) are the aforementioned
organic solvents, oils and fats.
[0787] Especially suitable cosmetically acceptable oil and fat
components c) are described in Karl-Heinz Schrader, Grundlagen und
Rezepturen der Kosmetika [Fundamentals and Formulations of
Cosmetics], 2nd edition, Verlag Huthig, Heidelberg, p. 319-355,
which is hereby incorporated by reference.
[0788] The cosmetic compositions of the invention may be
skin-cosmetic, hair-cosmetic, dermatological, hygiene or
pharmaceutical products.
[0789] The compositions of the invention may be in any form
suitable for ensheathing and/or coating by a multilayer film of the
invention. The compositions of the invention are preferably in the
form of a gel, ointment, cream, emulsion, suspension, lotion, milk
or paste. If desired, it is also possible to use liposomes or
microspheres.
[0790] The cosmetic compositions of the invention may additionally
comprise cosmetically and/or dermatologically active and effective
substances, and also auxiliaries. Preferably, the cosmetic
compositions of the invention comprise, as sheath and/or coating,
at least one multilayer film of the invention as defined above, at
least one carrier C) as defined above and at least one different
constituent preferably selected from cosmetically active
ingredients, emulsifiers, surfactants, preservatives, perfume oils,
bitter substances, additional thickeners, hair polymers, hair and
skin conditioners, graft polymers, water-soluble or dispersible
silicone-containing polymers, light stabilizers, bleaches, gel
formers, care agents, tints, tanning agents, dyes, pigments,
consistency regulators, humectants, refatting agents, collagen,
protein hydrolyzates, lipids, antioxidants, anti-yellowing agents,
defoamers, antistats, emollients and softeners.
[0791] The cosmetic active ingredients may comprise at least one
conventional thickener.
[0792] These include, for example, polysaccharides and organic
sheet minerals such as Xanthan Gum.RTM. (Kelzan.RTM. from Kelco),
Rhodopol.RTM. 23 (Rhone Poulenc) or Veegum.RTM. (from R. T.
Vanderbilt) or Attaclay.RTM. (from Engelhardt). Suitable thickeners
are also organic natural thickeners (agar-agar, carrageenan,
tragacanth, gum arabic, alginates, pectins, polyoses, guar flour,
carob seed flour, starch, dextrins, gelatin, casein) and inorganic
thickeners (polysilicic acids, clay minerals such as
montmorillonites, zeolites, silicas). Further thickeners are
polysaccharide gums, for example gum arabic, agar, alginates,
carrageenans and salts thereof, guar, guaran, tragacanth, gellan,
ramsan, dextran or xanthan and derivatives thereof, for example
propoxylated guar, and mixtures thereof. Other polysaccharide
thickeners are, for example, starches of a wide variety of
different origins and starch derivatives, for example hydroxyethyl
starch, starch phosphate esters or starch acetates, or
carboxymethyl cellulose or the sodium salt thereof, methyl
cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl
cellulose, hydroxypropyl methyl cellulose or hydroxyethyl methyl
cellulose, or cellulose acetate. The thickeners used may
additionally be sheet silicates. These include, for example, the
magnesium or sodium-magnesium sheet silicates obtainable under the
Laponite.RTM. trade name from Solvay Alkali, and the magnesium
silicates from Sud-Chemie.
[0793] Suitable cosmetically and/or dermatologically active
ingredients are, for example, skin and hair pigmentation agents,
tanning agents, bleaches, keratin-hardening substances,
antimicrobial active ingredients, photofilter active ingredients,
repellent active ingredients, hyperemic substances, keratolytic and
keratoplastic substances, antidandruff active ingredients,
antiphlogistics, keratinizing substances, antioxidative active
ingredients and active ingredients acting as free-radical
scavengers, skin moisturizing or humectant substances, regreasing
active ingredients, deodorizing active ingredients, sebostatic
active ingredients, plant extracts, antierythematous or
antiallergic active ingredients and mixtures thereof.
[0794] Artificial tanning active ingredients suitable for tanning
the skin without natural or artificial irradiation with UV rays
are, for example, dihydroxyacetone, alloxan and walnut shell
extract. Suitable keratin-hardening substances are generally active
ingredients as also used in antiperspirants, for example potassium
aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.
Antimicrobial active ingredients are used to destroy microorganisms
or to inhibit their growth and thus serve both as preservatives and
also as deodorizing substance which reduces the formation or the
intensity of body odor. These include, for example, customary
preservatives known to those skilled in the art, such as
p-hydroxybenzoic esters, imidazolidinylurea, formaldehyde, sorbic
acid, benzoic acid, salicylic acid, etc. Examples of such
deodorizing substances include zinc ricinoleate, triclosan,
undecylenic acid alkylolamides, triethyl citrate, chlorhexidine
etc. Suitable light filtering active ingredients are substances
which absorb UV rays in the UV-B and/or UV-A region. Suitable UV
filters are those mentioned above. Additionally suitable are
p-aminobenzoic esters, cinnamic esters, benzophenones, camphor
derivatives, and pigments which stop UV rays, such as titanium
dioxide, talc and zinc oxide. Suitable repellent active ingredients
are compounds capable of warding off or driving away certain
animals, particularly insects, from humans. These include, for
example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide etc.
Suitable substances with hyperemic activity, which stimulate blood
flow through the skin are, for example, essential oils, such as
dwarf pine, lavender, rosemary, juniperberry, roast chestnut
extract, birch leaf extract, hayseed extract, ethyl acetate,
camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil,
etc. Suitable keratolytic and keratoplastic substances are, for
example, salicylic acid, calcium thioglycolate, thioglycolic acid
and its salts, sulfur, etc. Suitable antidandruff active
ingredients are, for example, sulfur, sulfur polyethylene glycol
sorbitan monooleate, sulfur ricinol polyethoxylate, zinc
pyrithione, aluminum pyrithione, etc. Suitable antiphlogistics,
which counter skin irritations, are, for example, allantoin,
bisabolol, Dragosantol, camomile extract, panthenol, etc.
[0795] The cosmetic compositions of the invention may comprise, as
a cosmetic active (and optionally also as an auxiliary), at least
one cosmetically or pharmaceutically acceptable polymer. These
include, in quite general terms, anionic, cationic, amphoteric and
uncharged polymers.
[0796] Examples of anionic polymers are copolymers of acrylic acid
and acrylamide and salts thereof; sodium salts of
polyhydroxycarboxylic acids, water-soluble or water-dispersible
polyesters, polyurethanes, e.g. Luviset PUR.RTM. from BASF, and
polyureas. Particularly suitable polymers are copolymers of t-butyl
acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer.RTM.
100P), copolymers of ethyl acrylate and methacrylic acid (e.g.
Luvimer.RTM. MAE), copolymers of N-tert-butylacrylamide, ethyl
acrylate, acrylic acid (Ultrahold.RTM. 8, strong), copolymers of
vinyl acetate, crotonic acid and optionally further vinyl esters
(e.g. Luviset.RTM. products), maleic anhydride copolymers,
optionally reacted with alcohol, anionic polysiloxanes, e.g.
carboxy-functional, t-butyl acrylate, methacrylic acid (e.g.
Luviskol.RTM. VBM), copolymers of acrylic acid and methacrylic acid
with hydrophobic monomers, for example C.sub.4-C.sub.30-alkyl
esters of (meth)acrylic acid, C.sub.4-C.sub.30-alkyl vinyl esters,
C.sub.4-C.sub.30-alkyl vinyl ethers and hyaluronic acid. Another
example of an anionic polymer is the methyl
methacrylate/methacrylic acid/acrylic acid/urethane acrylate
copolymer obtainable under the Luviset.RTM. Shape name (INCI Name:
Polyacrylate-22). Further examples of anionic polymers are vinyl
acetate/crotonic acid copolymers, as commercially available, for
example, under the Resyn.RTM. (National Starch) and Gafset.RTM.
(GAF) names, and vinylpyrrolidone/vinyl acrylate copolymers
obtainable, for example, under the Luviflex.RTM. (BASF) trade name.
Further suitable polymers are the vinylpyrrolidone/acrylate
terpolymer available under the Luviflex.RTM. VBM-35 (BASF) name,
and sodium sulfonate-containing polyamides or sodium
sulfonate-containing polyesters. Additionally suitable are
vinylpyrrolidone/ethyl methacrylate/methacrylic acid copolymers, as
sold by Stepan under the Stepanhold-Extra and -R1 names, and the
Carboset.RTM. products from BF Goodrich.
[0797] Suitable cationic polymers are, for example, cationic
polymers having the INCI name Polyquaternium, e.g. copolymers of
vinylpyrrolidone/N-vinylimidazolium salts (Luviquat.RTM. FC,
Luviquat.RTM. HM, Luviquat.RTM. MS, Luviset Clear.RTM., Luviquat
Supreme.RTM., Luviquat.RTM. Care), copolymers of
N-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized
with diethyl sulfate (Luviquat.RTM. PQ 11), copolymers of
N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts
(Luviquat.RTM. Hold); cationic cellulose derivatives
(Polyquaternium-4 and -10), acrylamido copolymers
(Polyquaternium-7) and chitosan. Suitable cationic (quaternized)
polymers are also Merquat.RTM. (polymer based on
dimethyldiallylammonium chloride), Gafquat.RTM. (quaternary
polymers which form through reaction of polyvinylpyrrolidone with
quaternary ammonium compounds), polymer JR (hydroxyethyl cellulose
with cationic groups) and plant-based cationic polymers, e.g. guar
polymers, such as the Jaguar.RTM. products from Rhodia.
[0798] Very particularly suitable polymers are uncharged polymers
such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and
vinyl acetate and/or vinyl propionate, polysiloxanes,
polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone,
polyethyleneimines and salts thereof, polyvinylamines and salts
thereof, cellulose derivatives, polyaspartic salts and derivatives.
Examples of these include Luviflex.RTM. Swing (partly hydrolyzed
copolymer of polyvinyl acetate and polyethylene glycol, from
BASF).
[0799] Suitable polymers are also nonionic, water-soluble or
water-dispersible polymers or oligomers, such as
polyvinylcaprolactam, e.g. Luviskol.RTM. Plus (BASF SE), or
polyvinylpyrrolidone and copolymers thereof, especially with vinyl
esters such as vinyl acetate, e.g. Luviskol.RTM. VA 37, VA 55, VA
64, VA 73 (BASF SE); polyamides, for example based on itaconic acid
and aliphatic diamines, as described, for example, in DE-A-43 33
238.
[0800] Suitable polymers are also amphoteric or zwitterionic
polymers, such as the octyl acrylamide/methyl
methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl
methacrylate copolymers obtainable under the Amphomer.RTM. names
(National Starch), and zwitterionic polymers as disclosed, for
example, in German patent applications DE 39 29 973, DE 21 50 557,
DE 28 17 369 and DE 37 08 451. Acrylamidopropyltrimethylammonium
chloride/acrylic acid or methacrylic acid copolymers and alkali
metal and ammonium salts thereof are preferred zwitterionic
polymers. Further suitable zwitterionic polymers are
methacryloylethyl betaine/methacrylate copolymers, commercially
available under the Amersette.RTM. name (AMERCHOL), and copolymers
of hydroxyethyl methacrylate, methyl methacrylate,
N,N-dimethylaminoethyl methacrylate and acrylic acid
(Jordapon.RTM.).
[0801] Suitable polymers are also nonionic, siloxane-containing,
water-soluble or -dispersible polymers, for example
polyethersiloxanes such as Tegopren.RTM. (Goldschmidt) or
Belsil.RTM. (Wacker).
[0802] In a specific embodiment, the compositions of the invention
comprise at least one polymer which acts as a thickener.
[0803] Suitable polymeric thickeners are, for example, optionally
modified polymeric natural substances (carboxymethyl cellulose and
other cellulose ethers, hydroxyethyl and hydroxypropyl cellulose
and the like) and synthetic polymeric thickeners (polyacrylic and
polymethacrylic compounds, vinyl polymers, polycarboxylic acids,
polyethers, polyimines, polyamides). These include the polyacrylic
and polymethacrylic compounds, some of which have already been
mentioned above, for example the high molecular weight homopolymers
of acrylic acid crosslinked with a polyalkenyl polyether,
especially an allyl ether of sucrose, pentaerythritol or propylene
(INCI name: Carbomer). Polyacrylic acids of this kind are
obtainable, inter alia, from BF Goodrich under the Carbopol.RTM.
trade name, e.g. Carbopol 940 (molecular weight about 4 000 000
daltons), Carbopol 941 (molecular weight about 1 250 000 daltons)
or Carbopol 934 (molecular weight about 3 000 000 daltons). These
additionally include acrylic acid copolymers obtainable, for
example, from Rohm & Haas under the Aculyn.RTM. and Acusol.RTM.
trade names, for example the anionic, non-associative polymers
Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol
823 and Acusol 830 (CAS 25852-37-3). Also especially suitable are
associative thickeners, for example based on modified polyurethanes
(HEUR) or hydrophobically modified acrylic or methacrylic acid
copolymers (HASE thickeners, High Alkali Swellable Emulsion).
[0804] In a preferred embodiment, the compositions of the invention
are a skin cleanser.
[0805] Preferred skin cleansers are soaps of liquid to gel
consistency, such as transparent soaps, luxury soaps, deodorant
soaps, cream soaps, baby soaps, skin protection soaps, abrasive
soaps and syndets, pasty soaps, greasy soaps and washing pastes,
liquid washing, showering and bathing preparations, such as washing
lotions, shower baths and gels, foam baths, oil baths and scrub
preparations, shaving foams, lotions and creams.
[0806] In a further preferred embodiment, the compositions of the
invention are cosmetic compositions for care and protection of the
skin, nail care products or preparations for decorative
cosmetics.
[0807] More particularly, the skincare products according to the
invention are W/O or O/W skin creams, day and night creams, eye
creams, face creams, antiwrinkle creams, moisturizing creams,
bleaching creams, vitamin creams, skin lotions, care lotions and
moisturizing lotions.
[0808] Skin-cosmetic and dermatological compositions comprise
preferably at least one multilayer film of the invention in a
proportion of about 0.1% to 50% by weight, preferably 0.1% to 20%
by weight, based on the total weight of the composition.
[0809] The skincare compositions of the invention may take any form
suitable for ensheathing and/or coating by a multilayer film of the
invention, for example of a cream, foam, gel, stick, mousse, milk
or lotion.
[0810] As well as the polymer compositions P1) of the invention and
suitable carriers, the skin-cosmetic preparations may also comprise
further active ingredients and auxiliaries customary in skin
cosmetics, as described above. These preferably include
emulsifiers, preservatives, perfume oils, cosmetic active
ingredients such as phytantriol, vitamin A, E and C, retinol,
bisabolol, panthenol, light stabilizers, bleaches, tanning agents,
collagen, protein hydrolyzates, stabilizers, pH regulators, dyes,
salts, thickeners, gel formers, consistency regulators, silicones,
humectants, refatting agents and further customary additives.
[0811] Preferred oil and fat components of the skin-cosmetic and
dermatological products are the aforementioned mineral and
synthetic oils, for example paraffins, silicone oils and aliphatic
hydrocarbons having more than 8 carbon atoms, animal and vegetable
oils, for example sunflower oil, coconut oil, avocado oil, olive
oil, lanolin, or waxes, fatty acids, fatty acid esters, for example
triglycerides of C.sub.6-C.sub.30 fatty acids, wax esters, for
example jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin
and acetylated lanolin, and mixtures thereof.
[0812] It is also possible to blend the polymer composition P1) of
the invention with conventional polymers, as described above, if
specific properties are to be established.
[0813] To establish particular properties, for example improving
the tactile properties, the spreading characteristics, the water
resistance and/or the binding of active ingredients and
auxiliaries, such as pigments, the skin-cosmetic and dermatological
preparations may additionally also comprise conditioning substances
based on silicone compounds. Suitable silicone compounds are, for
example, polyalkylsiloxanes, polyarylsiloxanes,
polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
[0814] The cosmetic or dermatological preparations are produced by
customary methods known to those skilled in the art.
[0815] In a further preferred embodiment, the compositions of the
invention are a shower gel, a shampoo formulation or a bathing
preparation.
[0816] Formulations of this kind comprise at least one multilayer
film of the invention as a sheath and/or coating and typically
anionic surfactants as base surfactants and amphoteric and/or
nonionic surfactants as cosurfactants. Further suitable active
ingredients and/or auxiliaries are generally selected from lipids,
perfume oils, dyes, organic acids, preservatives and antioxidants,
and also thickeners/gel formers, skin conditioners and
moisturizers.
[0817] These formulations comprise preferably 2% to 50% by weight,
preferably 5% to 40% by weight, more preferably 8% to 30% by
weight, of surfactants, based on the total weight of the
formulation.
[0818] In the washing, showering and bathing preparations, it is
possible to use any of the anionic, uncharged, amphoteric or
cationic surfactants customarily used in personal care
products.
[0819] Suitable surfactants are those mentioned above.
[0820] In addition, the shower gel/shampoo formulations may
comprise further thickeners, for example sodium chloride, PEG-55,
propylene glycol oleate, PEG-120 methylglucose dioleate and others,
and also preservatives, further active ingredients and auxiliaries
and water.
[0821] In a further preferred embodiment, the compositions of the
invention are a hair treatment composition.
[0822] Hair treatment compositions of the invention preferably
comprise at least one multilayer film of the invention in an amount
in the range from about 0.1% to 50% by weight, preferably 0.1% to
20% by weight, based on the total weight of the composition.
[0823] Preferably, the hair treatment compositions of the invention
take the form of a hair mousse, hair gel, shampoo, end fluids,
neutralizer for permanent waves or hot-oil treatments. According to
the field of application, the hair-cosmetic preparations can be
applied in the form of a gel, cream, lotion or wax.
[0824] The multilayer films of the invention are especially
suitable as a sheath and/or coating for hairstyling formulations,
especially hair foams and hair gels.
[0825] Emulsifiers used may be any of the emulsifiers customarily
used in hair foams. Suitable emulsifiers may be nonionic, cationic
or anionic, or amphoteric.
[0826] The multilayer films of the invention are also suitable for
styling gels. Additional gel formers used may be any of the gel
formers customary in cosmetics. In this regard, reference is made
to the aforementioned conventional thickeners.
[0827] The multilayer films of the invention are also suitable for
shampoo formulations additionally comprising customary
surfactants.
[0828] To achieve certain effects, customary conditioners may be
used in the shampoo formulations. Examples of these include the
aforementioned cationic polymers with the INCI name Polyquaternium,
especially copolymers of vinylpyrrolidone/N-vinylimidazolium salts
(Luviquat.RTM. FC, Luviquat.RTM. HM, Luviquat.RTM. MS,
Luviquat.RTM. Care), copolymers of
N-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized
with diethyl sulfate (Luviquat.RTM. PQ 11), copolymers of
N-vinylcaprolactam/N-vinyl-pyrrolidone/N-vinylimidazolium salts
(Luviquat.RTM. Hold); cationic cellulose derivatives
(Polyquaternium-4 and -10), acrylamide copolymers
(Polyquaternium-7). In addition, it is possible to use protein
hydrolyzates, and conditioning substances based on silicone
compounds, for example polyalkylsiloxanes, polyarylsiloxanes,
polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
Further suitable silicone compounds are dimethicone copolyols
(CTFA) and aminofunctional silicone compounds such as
amodimethicones (CTFA). In addition, it is possible to use cationic
guar derivatives such as guar hydroxypropyltrimonium chloride
(INCI).
[0829] The multilayer films of the invention are likewise suitable
for use as a sheath and/or coating for pharmaceutical formulations
of any kind and in the coating of such pharmaceutical
formulations.
[0830] Typical pharmaceutical compositions comprise [0831] A) at
least one sheath and/or coating comprising or consisting of a
washing- and cleaning-active multilayer film as defined above, or
obtainable by a process as defined above, [0832] B) at least one
pharmaceutically acceptable active and [0833] C) optionally at
least one further pharmaceutically acceptable auxiliary other than
A) and B).
[0834] Pharmaceutically acceptable auxiliaries C) are auxiliaries
which are known to be usable in the field of pharmacy, food
technology and related fields, especially those listed in the
relevant pharmacopeias (e.g. DAB, Ph. Eur., BP, NF), and other
auxiliaries whose properties do not preclude a physiological
application.
[0835] Suitable auxiliaries C) may be: lubricants, wetting agents,
emulsifiers and suspension media, preservatives, antioxidants,
antiirritants, chelating agents, emulsion stabilizers, film
formers, gel formers, odor-masking agents, bitter substances,
resins, hydrocolloids, solvents, solubilizers, neutralizers,
permeation accelerators, pigments, quaternary ammonium compounds,
refatting and superfatting agents, ointment, cream or oil bases,
silicone derivatives, stabilizers, sterilizers, propellants,
desiccants, opacifiers, additional thickeners, waxes, plasticizers,
white oils. This kind of configuration is based on specialist
knowledge, as represented, for example, in Fiedler, H.P. Lexikon
der Hilfsstoffe fur Pharmazie, Kosmetik und angrenzende Gebiete
[Lexicon of Auxiliaries for Pharmacy, Cosmetics and Related
Fields], 4th ed., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.
[0836] To produce pharmaceutical compositions of the invention, the
active ingredients can be mixed or diluted with a suitable
excipient. Excipients may be solid, semisolid or liquid materials
which can serve as a vehicle, carrier or medium for the active.
Further auxiliaries are added, if desired, in the manner known to
the person skilled in the art. More particularly, these are aqueous
solutions or solubilizates for oral or parenteral administration.
Furthermore, the copolymers for use in accordance with the
invention are also suitable for use in oral administration forms
such as tablets, capsules, powders, solutions. Here, they can
provide the sparingly soluble drug with increased bioavailability.
In the case of parenteral administration, as well as solubilizates,
it is also possible to use emulsions, for example fatty
emulsions.
[0837] Pharmaceutical formulations of the type specified above can
be obtained by processing the polymer composition of the invention
with pharmaceutical active ingredients by conventional methods and
using known and new active ingredients.
[0838] The content of the at least one multilayer film of the
invention in the pharmaceutical compositions is preferably in the
range from 0.1% to 50% by weight, preferably 0.1% to 20% by weight,
based on the total weight of the composition.
[0839] For production of the pharmaceutical compositions of the
invention, all pharmaceutical active ingredients and prodrugs are
suitable in principle. These include benzodiazepines,
antihypertensives, vitamins, cytostatics, especially taxol,
anaesthetics, neuroleptics, antidepressants, antibiotics,
antimycotics, fungicides, chemotherapeutics, urologics, platelet
aggregation inhibitors, sulfonamides, spasmolytics, hormones,
immunoglobulins, sera, thyroid therapeutics, psychopharmaceuticals,
Parkinson's drugs and other antihyperkinetics, ophthalmics,
neuropathy preparations, calcium metabolism regulators, muscle
relaxants, narcotics, antilipemics, liver therapeutics, coronary
drugs, cardiac drugs, immunotherapeutics, regulatory peptides and
their inhibitors, hypnotics, sedatives, gynecological drugs, gout
remedies, fibrinolytics, enzyme preparations and transport
proteins, enzyme inhibitors, emetics, perfusion promoters,
diuretics, diagnostics, corticoids, cholinergics, biliary
therapeutics, antiasthmatics, broncholytics, beta-receptor
blockers, calcium antagonists, ACE inhibitors, arteriosclerosis
remedies, antiphlogistics, anticoagulants, antihypotensives,
antihypoglycemics, antihypertensives, antifibrinolytics,
antiepileptics, antiemetics, antidotes, antidiabetics,
antiarrhythmics, antianemics, antiallergics, anthelmintics,
analgesics, analeptics, aldosterone antagonists and slimming drugs.
Examples of suitable pharmaceutical active ingredients are
especially the active ingredients mentioned in paragraphs 0105 to
0131 of US 2003/0157170.
[0840] As well as for use in cosmetics and in pharmacy, the
multilayer films of the invention are also suitable as a sheath
and/or coating in the food and drink sector. In the context of the
present invention, food and drink preparations are also understood
to mean food supplements, for example preparations comprising food
and drink dyes and dietetic foods and drinks. In addition, the
polymer compositions P1) of the invention are also suitable for
feed supplements for animal nutrition.
[0841] The multilayer films of the invention are also suitable for
production of formulations of food supplements such as
water-insoluble vitamins and provitamins such as vitamin A, vitamin
A acetate, vitamin D, vitamin E, tocopherol derivatives such as
tocopherol acetate, and vitamin K.
[0842] Crop Protection Compositions
[0843] The multilayer film of the invention is also advantageously
suitable for ensheathing and/or coating of crop protection
compositions. It has been found that, surprisingly, the polymer
composition P1) of the invention in gel form has high compatibility
with a multitude of crop protection active ingredients and
adjuvants.
[0844] A preferred crop protection composition preferably comprises
the following constituents: [0845] at least one sheath and/or
coating comprising or consisting of a washing- and cleaning-active
multilayer film as defined above, or obtainable by a process as
defined above, [0846] at least one active, [0847] optionally at
least one adjuvant, [0848] optionally water, [0849] optionally at
least one thickener, and [0850] optionally at least one further
additive.
[0851] Suitable active ingredients for use in the crop protection
compositions of the invention are, for example, those which belong
to the group of the herbicides, fungicides, insecticides, growth
regulators, safeners, acaricides, molluscicides and
nematicides.
[0852] In many cases, the addition of adjuvants, for example of
oils, specific solvents, surfactants or surfactant mixtures, is
advantageous. In crop protection, adjuvants are auxiliaries which
increase the activity of an active (here: crop protection
compositions) and/or the selectivity thereof in relation to the
desired effect (for example fungicidal, insecticidal, herbicidal,
bactericidal, nematicidal, growth-regulating effect), but which
alone have only a very small effect, if any, in terms of crop
protection activity. The effect of adjuvants is in many cases based
on their interfacial activity, which improves contact of the
administration form of the active with the surface of the plant
and, by reducing the surface tension, improves the penetration of
the administration form and hence of the active into the soil.
[0853] The crop protection composition of the invention may be in
solid, liquid or gel form. The crop protection composition of the
invention may additionally comprise at least one thickener.
Suitable thickeners are those mentioned above as component E) for
the washing and cleaning compositions, to which reference is made
here in full. The crop protection composition of the invention
comprises the multilayer film of the invention preferably in an
amount of 0.1% to 50% by weight, more preferably of 0.1% to 20% by
weight, based on the total weight of the crop protection
composition.
[0854] The crop protection composition of the invention may
comprise further components. These include, for example,
dispersants, defoamers, preservatives, biocides, organic solvents,
antifreezes and the like.
[0855] Suitable dispersants or surfactants are preferably nonionic.
In principle, they may be similar in nature to the above-described
adjuvants, in which case they differ from the latter by a generally
higher molecular weight. Suitable molecular weights for dispersants
vary in the range from about 1000 g/mol (e.g. phosphated
tristyrylphenol ethoxylate, such as Soprophor 3D33 from Rhodia) up
to several thousand g/mol in the case of comb polymers (e.g. Atlox
4913 from Croda). Defoamers are preferably silicone-based
defoamers. A suitable preservative is, for example, dichlorophen.
Suitable biocides are, for example, isothiazolinones, such as
benzylisothiazolinone and methylisothiazolinone. Suitable
antifreezes are, for example, glycerol, ethylene glycol and
propylene glycol.
[0856] Similarly, it is also possible to produce veterinary
medicine administration forms, especially rumen-stable forms, and
also administration forms containing vitamins, carotenoids, trace
elements, nutraceuticals, amino acids and food supplements. The
latter can also serve as foods or supplements.
[0857] The invention is illustrated in detail by the examples
described hereinafter. At the same time, the examples should not be
regarded as a restriction of the invention.
EXAMPLES
[0858] All the examples for production of a polymer composition P1)
were created by the same general production method. The
individually produced polymer compositions of the invention are
referred to hereinafter as P1-1) to P1-6).
[0859] General Production Method for a Polymer Composition P1)
[0860] The initial charge was heated to 75.degree. C. while
stirring at 100 rpm. Then feeds 1, 2 and 3 were metered in within 4
h and the reaction mixture was polymerized for a further hour. The
mixture was then allowed to cool down to room temperature. The
polymer composition is obtained in the form of a transparent and
viscous solution.
[0861] The weight-average molecular weight M.sub.w of the polymer
composition P1) obtained was determined by means of gel permeation
chromatography (GPC) in aqueous solution using neutralized
polyacrylic acid as polymer standard. In this type of molecular
weight determination, the components of the polymer composition
which comprise the aforementioned monomers M) in copolymerized form
are ascertained. [0862] Standard: neutralized polyacrylic acid. The
calibration was carried out with narrow distribution Na-PAA
standards from PSS (Polymer Standards Service GmbH) with molecular
weights of M=1250 to M=1 100 000 g/mol. In addition, PAA standards
from the American Polymer Standards Corporation with molecular
weight M=1770 and M=900 g/mol were used. The values outside of this
elution range were extrapolated. [0863] Eluent: 0.01 mol/L
phosphate buffer pH=7.4 in distilled water with 0.01 M NaN.sub.3
[0864] Flow rate: 0.8 mL/min [0865] Amount injected: 100 .mu.L
[0866] Concentration: 1.5 mg/mL [0867] The sample solutions were
filtered through Millipore IC Millex-LG filters (0.2 .mu.m). [0868]
Column type: TSKgel GMPWXL [0869] Column set: 2 separation columns
(length=each 30 cm), exclusion limit 1000-8 000 000 g/mol
[0870] Detector: DRI Agilent 1200 UV Agilent 1200 VWD [260 nm]
[0871] Production of polymer composition P1-1)
TABLE-US-00001 Feedstock Amount (% by wt.) Content (%) Initial
charge Polyethylene glycol 24.48 100.00 Mw 1000 g/mol Water.sup.a)
16.78 100.00 Feed 1 acrylic acid 48.95 100.00 Feed 2
Initiator.sup.b) 0.35 100.00 Water.sup.a) 4.55 100.00 Feed 3
2-Mercaptoethanol 0.49 100.00 Sodium 1.34 55.00 hypophosphite
Water.sup.a) 3.07 100.00 .sup.a)demineralized water
.sup.b)2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No.
2997-92-4)
[0872] The weight-average molecular weight Mw of the polymer
composition P1-1) obtained was 11 800 g/mol.
[0873] Production of Polymer Composition P1-2)
TABLE-US-00002 Amount (% by Feedstock wt.) Content (%) Initial
charge Polyethylene oxide 24.48 100.00 having
C.sub.xH.sub.2x+1/C.sub.yH.sub.2y+1 termination at either end and
having a free OH group and x, y = 6 to 14 Water.sup.a) 16.78 100.00
Feed 1 acrylic acid 48.95 100.00 Feed 2 Initiator.sup.b) 0.35
100.00 Water.sup.a) 4.55 100.00 Feed 3 2-Mercaptoethanol 0.49
100.00 Sodium 1.34 55.00 hypophosphite Water.sup.a) 3.07 100.00
.sup.a)demineralized water
.sup.b)2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No.
2997-92-4)
[0874] The weight-average molecular weight Mw of the polymer
composition P1-2) obtained was 11 100 g/mol.
[0875] Production of Polymer Composition P1-3)
TABLE-US-00003 Amount (% by Feedstock wt.) Content (%) Initial
charge C.sub.13C.sub.15 alcohol + 9 EO + 24.08 100.00 2 BuO
Water.sup.a) 18.12 100.00 Feed 1 acrylic acid 48.17 100.00 Feed 2
Initiator.sup.b) 0.34 100.00 Water.sup.a) 4.47 100.00 Feed 3
2-Mercaptoethanol 0.96 100.00 Sodium 2.63 55.00 hypophosphite
Water.sup.a) 1.23 100.00 .sup.a)demineralized water
.sup.b)2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No.
2997-92-4)
[0876] The weight-average molecular weight Mw of the polymer
composition P1-3) obtained was 6120 g/mol.
[0877] Production of Polymer Composition P1-4)
TABLE-US-00004 Content Feedstock Amount (% by wt.) (%) Initial
charge C.sub.13C.sub.15 alcohol + 9 EO + 17.98 100.00 2 BuO
Water.sup.a) 18.09 100.00 Feed 1 Acrylic acid 53.94 100.00 Feed 2
Initiator.sup.b) 0.38 100.00 Water.sup.a) 4.61 100.00 Feed 3
2-Mercaptoethanol 1.08 100.00 Sodium 2.94 55.00 hypophosphite
Water.sup.a) 0.97 100.00 .sup.a)demineralized water
.sup.b)2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No.
2997-92-4)
[0878] The weight-average molecular weight Mw of the polymer
composition P1-4) obtained was 6270 g/mol.
[0879] Production of Polymer Composition P1-5)
TABLE-US-00005 Amount (% by Feedstock wt.) Content (%) Initial
charge Polyethylene oxide 24.48 100.00 having CXH2X + 1/ CyH2y + 1
termination at either end and having a free OH group and x, y = 6
to 14 Water.sup.a) 16.78 100.00 Feed 1 Acrylic acid 32.38 100.00
Methacrylic acid 16.58 100.00 Feed 2 Initiator.sup.b) 0.35 100.00
Water.sup.a) 4.55 100.00 Feed 3 2-Mercaptoethanol 0.49 100.00
Sodium 1.34 55.00 hypophosphite Water.sup.a) 3.07 100.00
.sup.a)demineralized water
.sup.b)2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No.
2997-92-4)
[0880] The weight-average molecular weight Mw of the polymer
composition P1-5) obtained was 15 700 g/mol.
[0881] Production of Polymer Composition P1-6
TABLE-US-00006 Feedstock Amount (% by wt.) Content (%) Initial
Polyethylene oxide 24.48 100.00 charge having CXH2X + 1/ CyH2y + 1
termination at either end and having a free OH group and x, y = 6
to 14 Water.sup.a) 4.00 100.00 Feed 1 2-Acrylamido-2- 25.57 50.00
methylpropanesulfonic acid sodium salt Acrylic acid 36.17 100.00
Feed 2 Initiator.sup.b) 0.35 100.00 Water.sup.a) 4.55 100.00 Feed 3
2-Mercaptoethanol 0.49 100.00 Sodium hypophosphite 1.34 55.00
Water.sup.a) 3.07 100.00 .sup.a)demineralized water
.sup.b)2,2'-azobis(2-methylpropionamidine) dihydrochloride (CAS No.
2997-92-4)
[0882] The weight-average molecular weight Mw of the polymer
composition P1-6) obtained was 13 000 g/mol.
[0883] Production of an Application Solution A1-A3 for Film Layers
of Polyvinyl Alcohol (PVOH Films):
[0884] 20 g of a solid polyvinyl alcohol were dissolved in 80 g of
deionized water at 60.degree. C. while stirring. 5.0 g of glycerol
were added to 100 g of the polyvinyl alcohol solution thus
prepared. The solution was heated to 80.degree. C. Subsequently, by
addition of deionized water, the polyvinyl alcohol concentration of
the solution was adjusted to 18.0% by weight. The polyvinyl alcohol
application solution was mixed well and heated at 80.degree. C.
until the air stirred in had escaped completely. [0885] A1:
polyvinyl alcohol=Poval.RTM. 26-88 from Kuraray, nonvolatile
components: 97.5% [0886] A2: polyvinyl alcohol=Poval.RTM. 40-88
from Kuraray, nonvolatile components: 97.5% [0887] A3: polyvinyl
alcohol=Poval.RTM. 8-88 from Kuraray, nonvolatile components:
97.5%
[0888] Production of an Application Solution A4 for Film Layers of
Polyvinyl Alcohol (PVOH Films):
[0889] 20 g of a solid polyvinyl alcohol (Poval.RTM. 26-88 from
Kuraray, nonvolatile components: 97.5%) were dissolved in 80 g of
deionized water at 60.degree. C. while stirring. 2.0 g of glycerol
and 0.20 g of a C.sub.13C.sub.15 oxo process alcohol with 7 EO were
added to 100 g of the polyvinyl alcohol solution thus prepared. The
solution was heated to 80.degree. C. Subsequently, by addition of
deionized water, the polyvinyl alcohol concentration of the
solution was adjusted to 18.0% by weight. The polyvinyl alcohol
application solution was mixed well and heated at 80.degree. C.
until the air stirred in had escaped completely.
[0890] Production of an Application Solution B1 for Film Layers of
the Polymer Composition P1-1):
[0891] 100 g of the polymer composition P1-1) were heated to
80.degree. C. After addition of 4.2 g of glycerol, the
concentration of the polymer composition was diluted to 65% by
weight with deionized water. The application solution was mixed
well and heated at 60.degree. C. until the air stirred in had
escaped completely.
[0892] Production of an Application Solution B2 for Film Layers of
the Polymer Composition P1-2):
[0893] 100 g of the polymer composition P1-2) were heated to
80.degree. C. Thereafter, the concentration of the polymer
composition was diluted to 73% by weight with deionized water. The
application solution was mixed well and heated at 60.degree. C.
until the air stirred in had escaped completely.
[0894] Production of an Application Solution B3 for Film Layers of
the Polymer Composition P1-3):
[0895] 100 g of the polymer composition P1-3) were heated to
80.degree. C. After addition of 4.2 g of glycerol, the
concentration of the polymer composition was diluted to 65% by
weight with deionized water. The application solution was mixed
well and heated at 60.degree. C. until the air stirred in had
escaped completely.
[0896] Production of an Application Solution B4 for Film Layers of
the Polymer Composition P1-4):
[0897] 100 g of the polymer composition P1-4) were heated to
80.degree. C. After addition of 7.0 g of glycerol, the
concentration of the polymer composition was diluted to 65% by
weight with deionized water. The application solution was mixed
well and heated at 60.degree. C. until the air stirred in had
escaped comp